Liquid crystalline compound and liquid crystal composition containing the same

ABSTRACT

A liquid crystalline compound expressed by the general formula (1) ##STR1## (wherein R 1  is an alkyl group having 1 to 12 carbon atoms and one CH 2  group in the alkyl group may be replaced by oxygen atom or --CH═CH--; X represents hydrogen atom or fluorine atom; Y represents hydrogen atom or alkoxy group having 1 to 5 carbon atoms; l and m independently represent 0 or 1, respectively; and n and p independently represent an integer of 0 to 10, respectively, and when p is 0, n is 1 or more, and when Y is an alkoxy group, X is a fluorine atom and p is 0.) 
     Liquid crystal compositions which are suitable for use in liquid crystal display devices, have a high clearing point, and have a function of decreasing viscosity, and novel liquid crystalline compounds useful as a component of the liquid crystal compositions are provided.

This application is a 371 of PCT/JP94/01914 filed Nov. 11,1994.

FIELD OF TECHNOLOGY

The present invention relates to a liquid crystalline compound andliquid crystal composition. More specifically, the present inventionrelates to a novel liquid crystalline compound having a groupsubstituted with fluorine at the end of the molecule and a liquidcrystal composition containing the same.

BACKGROUND TECHNOLOGY

Liquid crystal compositions, particularly nematic liquid crystalcompositions are widely used for display materials, for example, indisplays such as watches, tabletop calculators, word-processors,computer terminals, and televisions. Driving mode of liquid crystaldisplay devices using a nematic liquid crystal composition is roughlyclassified into three kinds of modes such as twisted nematic (TN), supertwisted nematic (STN), and thin film transistor driving.

While a suitable driving mode is selected according to application, itis necessary in any method that response speed to field inversion ishigh to realize an excellent displaying capability.

In order to actualize a high response speed to field, it is necessarythat the viscosity of liquid crystal composition is low. That is, it isimportant to use a liquid crystal composition having a low viscosity. Inorder to achieve this object, attempts have been made in which abicyclohexane type compound or cyclohexylethyl cyclohexane type compoundwhich is known as a low viscosity liquid crystal compound is used as aconstituent (hereinafter referred to as viscosity decreasing agent) ofliquid crystal compositions to decrease the viscosity (for example,Examined Japanese Patent Publication No. 05-020418, Examined JapanesePatent Publication No. 62-015052, Unexamined Japanese Patent PublicationNo. 59-70624, and WO 90/01056). However, such bicyclic cyclohexane typecompounds have a disadvantage that clearing point (temperature at whicha liquid crystal phase or crystal becomes an isotropic liquid) is low.When the decrease in viscosity of the compositions is intended, theamount of viscosity decreasing agent to be used is as much as severaltens percent, and as the result, mesomorphic range of liquid crystalcompositions is remarkably decreased. Consequently, it is conceivable tostart from bicyclohexane type compounds or cyclohexylethyl cyclohexanetype compounds having a function of decreasing viscosity and derivingthem to liquid crystalline compounds which additionally have a highclearing point. However, efficient methods for the derivation have notyet been known.

Heretofore, compounds in which fluorine atoms are introduced in such agroup as a side chain alkyl group at the end of a molecule, for example,compounds in which three or more fluorine atoms are introduced in a sidechain alkyl group (DE 4101600), compounds in which a plural number ofdifluoromethylene groups are introduced (DE 4034123), and compounds inwhich fluorine atoms are introduced at the central bonding part (DE4023106 and DE 4015681) are known. However, these compounds are notrelated to bicyclohexane type compounds nor cyclohexylethyl cyclohexanetype compounds. Besides, these compounds do not lead to a rise in theclearing point.

Further, there have been proposed many applications in which compoundshaving a fluoroalkyl group are recited in their claims (for example,Unexamined Japanese Patent Publication Nos. 1-135745 and 3-153670).However, there is no case in which such compounds are actually preparedand their physical properties of the compounds are studied.

DISCLOSURE OF THE INVENTION

An object of the present invention is to overcome the defects in theprior art mentioned above and to provide bicyclohexane type compounds orcyclohexylethyl cyclohexane compounds which can raise the clearing pointof liquid crystal compositions while maintaining viscosity decreasingfunction when used as a component of liquid crystal compositions, and toprovide liquid crystal compositions containing the compounds.

The present invention which is to achieve the objects mentioned aboveand claimed by the present application is summarized as follows:

(1) A liquid crystalline compound expressed by the general formula (1)##STR2## (wherein R₁ is an alkyl group having 1 to 12 carbon atoms andone CH₂ group in the alkyl group may be replaced by oxygen atom or--CH═CH--; X represents hydrogen atom or fluorine atom; Y representshydrogen atom or alkoxy group having 1 to 5 carbon atoms; Q and mindependently represent 0 or 1, respectively; and n and p independentlyrepresent an integer of 0 to 10, respectively, and when p is 0, n is 1or more, and when Y is an

alkoxy group, X is fluorine atom and p is 0.)

(2) A liquid crystalline compound recited in (1) wherein m is 0.

(3) A liquid crystalline compound recited in (1) wherein m is 1.

(4) A liquid crystalline compound recited in (1) wherein Y is hydrogenatom.

(5) A liquid crystalline compound recited in (1) wherein Y is an alkoxygroup.

(6) A liquid crystalline compound recited in (2) wherein p is 0.

(7) A liquid crystalline compound recited in (2) wherein p is 1.

(8) A liquid crystalline compound recited in (3) wherein p is 0.

(9) A liquid crystalline compound recited in (3) wherein p is 1.

(10) A liquid crystal composition comprising two or more components andcontaining, as component, at least one compound recited in any one ofthe items (1) to (9) mentioned above.

(11) A liquid crystal composition containing, as a first component, atleast one compound recited in any one of the items (1) to (9) mentionedabove and containing, as a second component, one or more compoundsselected from the group consisting of the following general formulas(II), (III), and (IV) ##STR3## (wherein R₂ represents an alkyl grouphaving 1 to 10 carbon atoms, Z represents F or Cl, Q₁ and Q₂independently represent H or F, respectively, r represents 1 or 2, andZ₁ and Z₂ independently represent --CH₂ CH₂ -- or covalent bond.)

(12) A liquid crystal composition containing, as a first component, atleast one compound recited in any one of the items (1) to (9) mentionedabove, and containing, as a second component, one or more compoundsselected from the group consisting of the following general formulas(V), (VI), (VII), (VIII), and (IX) ##STR4## (wherein R₃ represents analkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to10 carbon atoms, methylene groups which are not adjacent to each otherin these groups may be replaced by oxygen atom, Z₃ represents --CH₂ CH₂--, --COO--, or covalent bond, Q₃ represents H or F, A represents acyclohexane ring, benzene ring, or 1,3-dioxane ring, and s represents 0or 1.) ##STR5## (wherein R₄ represents an alkyl group having 1 to 10carbon atoms, Q₄ represents H or F, and k represents 0 or 1.) ##STR6##(wherein R₅ represents alkyl group having 1 to 10 carbon atoms, Brepresents cyclohexane ring or benzene ring, Q₅ represents H or F, Z₄represents --COO-- or covalent bond, and h represents 0 or 1.) ##STR7##(wherein R₆ and R₇ independently represent an alkyl group, alkoxy group,or alkoxymethyl group each having 1 to 10 carbon atoms, K representscyclohexane ring, pyrimidine ring, or benzene ring, D representscyclohexane ring or benzene ring, and Z₅ represents --C.tbd.C--,--COO--, --CH₂ CH₂ --, or covalent bond.) ##STR8## (wherein R₈represents an alkyl group or alkoxy group each having 1 to 10 carbonatoms, R₉ represents an alkyl group, alkoxy group, or alkoxymethyl groupeach having 1 to 10 carbon atoms, E represents cyclohexane ring orpyrimidine ring, G and J independently represent cyclohexane ring orbenzene ring, respectively, Z₆ independently represents --COO--, --Ch₂CH₂ --, or covalent bond, respectively, Z₇ represents --C.tbd.C--,--COO--, or covalent bond, and Q₆ represents H or F.)

(13) A liquid crystal display device composed by using a liquid crystalcomposition comprising 2 or more components and containing, ascomponent, at least one compound recited in any one of the items (1) to(9) mentioned above.

(14) A liquid crystal display device composed by using a liquid crystalcomposition recited in any one of the items (10) to (12) mentionedabove.

BEST MODE FOR CONDUCTING THE INVENTION

Liquid crystalline compounds expressed by the general formula (1) in thepresent invention are characterized by having a fluoroalkyl orfluoroalkoxy group expressed by the following formula at the end of themolecule: ##STR9## (wherein m, n, p, X, and Y are the same as thosementioned above).

Clearing point is raised by introducing the group mentioned above at theend of the molecule. Among the compounds of the formula (1), onesexhibiting particularly preferable characteristics are roughlyclassified into the following 10 groups of (1a) to (1k): ##STR10##(wherein n is the same as that mentioned above, R is an alkyl grouphaving 1 to 5 carbon atoms, q is an integer of 1 to 10, Q is4-(4-substituted cyclohexyl)cyclohexyl group or 4-(2-(4-substitutedcyclohexyl)ethyl)cyclohexyl group.)

That is, the compounds of the present invention are roughly classified,in reference to the substituent at the end of the molecule mentionedabove, into groups (1a) and (1e) which have a difluoromethylene groupwithin alkyl groups or alkoxy groups; (1b) and (1f) which have adifluoromethyl group at the end; (1c) and (1g) which have amonofluoromethylene group in the substituent group; (1d) and (1h) whichhave a monofluoromethyl group at the end; and (1j) and (1k) which havean alkoxy substituted difluromethyl group at the end.

Most of the compounds of the present invention exhibit a smectic phase.Whereas liquid crystal compositions used for display devices are oneshaving a nematic phase, when mixed with nematic liquid crystalcompounds, the compounds of the present invention do not produce suchinjurious effects as of decreasing the temperature range of nematicphase. Thus, the compounds of the present invention are suitable andpreferable as constituent for nematic liquid crystal compositions.

Since the compounds of the present invention are extremely stable inchemical nature and not deteriorated by the effects of heat, ultravioletray, and electric field, they are preferable as a constituent ofelectrooptical devices.

Compounds expressed by the formula (1) in the present invention areproduced by the following methods depending on the values and groupsadopted for m, p, and X, respectively:

Abbreviations used in the description hereinafter have meanings asfollows:

    ______________________________________                                        DAST:        Diethylaminosulfur trifluoride                                   LAH:         Aluminum lithium hydride                                         SBH:         Sodium boron hydride                                             HFP-ET.sub.2 NH:                                                                           Hexafluoropropene diethylamine                                   DAIBAL:      Aluminum diisobutyl hydride                                      PCC:         Pyridiumchlorochromate                                           Lawson reagent:                                                                            2,4-bis (4-methoxyphenyl)-1,3-dithia-2,4-                                     diphosphethane-2,4-disulfide                                     PDC:         Pyridiumdichromate                                               ______________________________________                                    

Production of the compounds ((1a) and (1c)) wherein m is 0, p or q is 1or more, Y is hydrogen atom:

The compounds can be produced according to the following scheme:##STR11## (In the description above, Q and n show the same meanings asdescribed before.)

That is, when n is 1 or more, (3) is obtained by subjecting cyclohexanecarboxylic acids (2) produced according to the method of Krause et al.(U.S. Pat. No. 4,229,315) to a carbon increasing reaction. A ketone (4)is obtained by converting (3) to an acid halide with a halogenatingreagent such as thionyl chloride and reacting with alkylmagnesium halidein the presence of a catalyst according to a method of Fiandaneze et al.(Tetrahedron Letters, 25, 4805 (1984)). (4) is converted to acorresponding (1a) by reacting with a fluorinating agent such as DAST(W. H. Midleton et al., Journal of the Organic Chemistry, 40, 574(1975)), MQF₆ (F. Massey et al., Tetrahedron, 31,391 (1975), SeF₄ (G. A.Oller et al., Journal of the American Chemical Society, 96, 925 (1974)),SF₄ (G. A. Bozwell et al., Organic Reactions, 21, 1 (1974)), and CF₂ BR₂/Zn (C. M. Hume et al., Journal of the Chemical Society Parkin Trans,1,335 (1993)). Fluorination of carbonyl groups can also be performed byconverting carbonyl compounds to more reactive derivatives andfluorinating them. That is, methods passing through hydrazones (S. Rosenet al., Journal of the American Chemical Society, 109, 896 (1987), G. K.S. Plakash et al., Synlet, 594 (1990), T. B. Patrick, Journal of theFluorine Chemistry, 157 (1983)), a method through diazo compounds (T. B.Patrick et al., Journal of the Organic Chemistry, 46, 3917 (1981)), amethod through 1,3-dithiolane (S. C. Sonji et al., Journal of theOrganic Chemistry, 51,3508 (1986)), and a method throughgeminaldihalogen compounds (A. J. Bladworth et al., Tetrahedron Letters,5347 (1987)) are preferably used. On the other hand, when n is 0, (2)may be converted to a ketone (4) by directly converting (2) to an acidhalide with a halogenating reagent such as thionyl chloride and thenreacting with alkylmagnesium halide in the presence of a catalyst. Also,(1c) can be produced by reducing (4) with a reducing agent such as LAHand SBH to form an alcohol (5) and then fluorinating hydroxyl group witha fluorinating agent. In this case, DAST and HFP-ET₂ NH are preferableas fluorinating agent to be used (N. Ishikawa et al., Bulletin ChemicalSociety of Japan, 52, 3377 (1979). Further, (3) can also be obtained byconverting a cyclohexanone (6) to an unsaturated ester by Wittigreaction (for instance, O. Isler et al., Helvetica Chimica Acta, 40,1242 (1957)) or by a method of Emmons et al. (Organic Synthesis V, 547(1973)), and then subjecting unsaturated parts to a hydrogenation.

Production of the compounds ((1b) and (1d)) wherein m is 0, p is 0, andY is a hydrogen atom:

The compounds can be produced according to the following scheme:##STR12## (In the description above, Q and n show the same meanings asdescribed before.)

That is, (1b) is obtained be deriving a carboxylic acid (3) to analdehyde (7) and then fluorinating it by the same method as mentionedbefore. Whereas (7) is preferably synthesized by using DAIBAL accordingto the method, for example, of Zakhalkin et al. (Tetrahedron Letters,619 (1962)), it can also be obtained by reducing (3) to form an alcohol,and further oxidizing it with an oxidizing agent such as PCC. Further,(1d) can be produced by reducing (3) with a reducing agent such as LAHand SBH to form an alcohol (8) and then fluorinating a hydroxyl groupwith a fluorinating agent mentioned before.

Production of the compounds ((1e) and (1g)) wherein m is 1, p or q is 1or more, and Y is hydrogen atom:

The compounds can be produced according to the following scheme:##STR13## (In the description above, Q, n, and q show the same meaningsas described before.)

That is, a ketal such as (10) is obtained by reducing a cyclohexanonederivative (6) with a reducing agent such as LAH and SBH to convert intoa cyclohexal derivative (9) and then reacting with an alkyl halide. (1e)can be produced (when n is 1 or more) by separating a protective groupto form (11) and then fluorinating it with a fluorinating agentmentioned before. Further, (1g) can be produced by reducing (11) with areducing agent such as LAH and SBH to form an alcohol (12) and thenfluorinating hydroxyl group with a fluorinating agent mentioned before.In this case, when n is 0, since (11) is an ester, it is preferable toconvert it into a thioester (13) with a Lawson reagent (Synthesis, 941(1979)) and then fluorinating it with DAST to obtain (1e).

Production of the compounds ((1f) and (1h)) wherein m is 1, p is 0, andY is a hydrogen atom:

The compounds can be produced by the following scheme: ##STR14## (In thedescription above, Q and n show the same meanings as described before.)

That is, (14) is obtained by reacting a cyclohexanol derivative (9) withan alkyl halide. (1f) can be produced by separating a protective groupto convert it into an aldehyde (15) and then fluorinating with afluorinating agent mentioned before. Further, (1h) can be produced byreducing (15) with a reducing agent such as LAH and SBH to form analcohol (16) and then fluorinating hydroxyl group with a fluorinatingagent mentioned before. When n is 1 or 2 in this procedure, as adifferent method, an alcohol (16) can be obtained by reacting acyclohexanone derivative (6) with ethylene glycol or 1,3-propanediol toconvert into a spiroketal (17) and then reducing it with LAH in thepresence of a Lewis acid according to the method of Dygenote et al.(Organic Synthesis V. 303 (1973)). Further, an aldehyde (15) can beobtained by oxidizing (16) with PCC or another compound.

Production of the compounds ((ij) and (1k)) wherein m is 0 or 1, X is afluorine atom, p is 0, and Y is an alkoxy group:

The compounds can be produced by the following scheme: ##STR15## (In thedescription above, Q, n, and R show the same meanings as describedbefore.)

That is, (20) is obtained by deriving a carboxylic acid (3) orcarboxylic acid (18) obtained by oxidizing an alcohol (16) with PDC toan ester (19), and then treating it with a Lawson reagent. (1j) and (1k)are obtained by fluorinating (20) thus obtained with a fluorinatingagent mentioned before.

Compounds (1) of the present invention produced by such methodsmentioned above are remarkably excellent as constituent for nematicliquid crystal compositions. That is, the compounds can provide nematicliquid crystal compositions suitable for electrooptical devices sincethe compounds have excellent characteristics mentioned before andbesides, they are readily miscible with several liquid compounds. Suchliquid crystal compositions are preferably achieved by mixing a compoundoptionally selected, depending on the purpose, from a group of compounds(B) having a Δε of ≧5, a group of compounds (C) having a |Δε| of <5,particularly a group of compounds (D) having a clearing point of 80° C.or higher, and a group of other compounds (E) to a component (A)containing at least one compounds (1).

Following compounds can preferably be mentioned as ones included in (B),(C), (D), or (E). That is, the following (B1) to (B13) can be statedfirst as the compounds included in (B): ##STR16## (In the descriptionabove, whereas Ra represents an alkyl group or alkenyl group having 1 to10 carbon atoms, a carbon atom, or two or more carbon atoms which arenot adjacent to each other in the group may be substituted with oxygenatom.)

The following (C1) to (C34) can be mentioned as the compoundscorresponding to (C): ##STR17## (In the description above, whereas Raand Ra' independently represents an alkyl group or alkenyl group having1 to 10 carbon atoms, respectively, one carbon atom, or two or morecarbon atoms which are not adjacent to each other in the group may be 5substituted with oxygen atom.) The following (D1) to (D57) can bementioned as the compounds corresponding to (D): ##STR18## (In thedescription above, Ra and Ra' show the same meanings as describedbefore.)

The following (E1) to (E18) can be mentioned as the compoundscorresponding to (E): ##STR19## (In the description above, Ra and Ra'show the same meanings as described before.)

Liquid crystal composition of the present invention preferably containsat least one compound expressed by (1) in a ratio of 0.1 to 80% byweight to develop excellent characteristics.

Liquid crystal composition of the present invention has a widemesomorphic range. Besides, when used for STN or TN liquid crystaldisplay devices, they can achieve improvements in steepness and viewingangle. Also, since the compounds of formula (1) have a low viscosity,liquid crystal display devices using the compounds are improved in theirresponse speed.

The following can be mentioned as examples of the liquid crystalcomposition of the present invention, particularly as the examples ofnematic liquid crystal compositions. In these examples of thecomposition, No. of the compounds is the same as that shown in theExamples described below:

Example of Composition 1

4-(4-propylcyclohexyl)-(1,1-difluorobutyl)cyclohexane (Compound No. 3)10%

4-(4-propylcyclohexyl)-(1,1-difluoropentyl)cyclohexane (Compound No. 4)10%

1,2,3-trifluoro-5-(4-heptylcyclohexyl)benzene 5%

1,2-difluoro-4-(4-(4-ethylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4-(4-(4-pentylcyclohexyl)cyclohexyl)benzene 7%

1,2,3-trifluoro-5-(4-(2-(4-propylcyclohexyl)ethyl) cyclohexyl)benzene 9%

1,2,3-trifluoro-5-(4-(2-(4-pentylcyclohexyl)ethyl) cyclohexyl)benzene 5%

1,2,3-trifluoro-5-(2-(4-(4-propylcyclohexyl)cyclohexyl) ethyl)benzene 8%

1,2,3-trifluoro-5-(2-(4-(4-pentylcyclohexyl)cyclohexyl) ethyl)benzene 7%

1,2,3-trifluoro-5-(4-(4-propylcyclohexyl)cyclohexyl)benzene 8%

1,2,3-trifluoro-5-(4-(4-pentylcyclohexyl)cyclohexyl)benzene 7%

4-(4-(4-propylcyclohexyl)cyclohexyl)-fluorobenzene 5%

4'-(4-propylcyclohexyl)-4-fluorobiphenyl 5%

The composition mentioned above exhibits the value of physicalproperties as follows:

Clearing point:80.8° C., Δε:4.7, Δn:0.0689, viscosity:24.9 cP, thresholdvoltage at a cell thickness of 8.7 μ: 2.02 V

Example of Composition 2

4-4(propylcyclohexyl)-(2, 2-difluoropentyl)cyclohexane (Compound No. 6)8%

4-4(propylcyclohexyl)-(3,3-difluoropentyl)cyclohexane (Compound No. 7)7%

1,2-difluoro-4-(4-heptylcyclohexyl)benzene 5%

1,2-difluoro-4-(2-(4-pentylcyclohexyl)ethyl)benzene 5%

1,2-difluoro-4'-(4-ethylcyclohexyl)biphenyl 5%

1,2-difluoro-4'-(4-propylcyclohexyl)biphenyl 5%

1,2-difluoro-4'-(4-pentylcyclohexyl)biphenyl 10%

1,2-difluoro-4-(4-(2-(4-ethylcyclohexyl)ethyl)cyclohexyl) benzene 10%

1,2-difluoro-4-(4-(2-(4-propylcyclohexyl)ethyl)cyclohexyl) benzene 5%

1,2-difluoro-4-(4-(2-(4-pentylcyclohexyl)ethyl)cyclohexyl) benzene 10%

4-(4-pentylcylcohexyl)-chlorobenzene 5%

4-(4-hexylcyclohexyl)-chlorobenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-chlorobenzene 5%

4-(4-(4-pentylcyclohexyl)cyclohexyl)-chlorobenzene 5%

1,2,3-trifluoro-5-(4-(4-propylcyclohexyl)cyclohexyl)benzene 5%

1,2,3-trifluoro-5-(4-(4-pentylcyclohexyl)cyclohexyl)benzene 5%

The composition mentioned above exhibits the values of physicalproperties as follows:

Clearing point:71.5° C., Δε:4.0, Δn:0.0829, viscosity:20.0 cP, thresholdvoltage at a cell thickness of 8.8 μ:2.18 V

Example of Composition 3

4-(4-pentylcyclohexyl)-(2, 2-difluorobutyl)cyclohexane (Compound No. 14)10%

4-(4-pentylcyclohexyl)-(2-fluorobutyl)cyclohexane (Compound No. 60) 10%

1,2-difluoro-4-(2-(4-pentylcyclohexyl)ethyl)benzene 9%

1,2-difluoro-4-(4-(4-ethylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4-(4-(4-pentylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4'-(4-ethylcyclohexyl)biphenyl 5%

1,2-difluoro-4'-(4-propylcyclohexyl)biphenyl 5%

1,2-difluoro-4'-(4-pentylcyclohexyl)biphenyl 10%

4-fluorophenyl 4-pentylcyclohexylcarboxylate 7%

4-fluorophenyl 4-heptylcyclohexylcarboxylate 8%

4-(4-(4-propylcyclohexyl)cyclohexyl-methylbenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl-propylbenzene 5%

1-chloro-2-fluoro-4-(4-(2-(4-propylcyclohexyl)ethyl) cyclohexyl)benzene5%

Example of Composition 4

4-(4-(1-butenyl)cyclohexyl)-1-(3-fluoropropyl)cyclohexane (Compound No.255) 7%

4-(4-(3-butenyl)cyclohexyl)-1-(3-fluoropropyl)cyclohexane (Compound No.256) 8%

1,2-difluoro-4-(4-(4-ethylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4-(4-(4-pentylcyclohexyl)cyclohexyl)benzene 7%

4'-(4-ethylcyclohexyl)-3,4-difluorobiphenyl 5%

4'-(4-propylcyclohexyl)-3,4-difluorobiphenyl 5%

4'-(4-pentylcyclohexyl)-3,4-difluorobiphenyl 10%

1,2,3-trifluoro-5-(4-(4-propylcyclohexyl)cyclohexyl)benzene 9%

1,2,3-trifluoro-5-(4-(4-pentylcyclohexyl)cyclohexyl)benzene 5%

4'-(4-propylcyclohexyl)-3,4,5-trifluorobiphenyl 5%

4'-(4-pentylcyclohexyl)-3,4,5-trifluorobiphenyl 5%

1,2,3-trifluoro-5-(4-(2-(4-propylcyclohexyl)ethyl) cyclohexyl)benzene 5%

1,2,3-trifluoro-5-(4-(2-(4-pentylcyclohexyl)ethyl) cyclohexyl)benzene 5%

1,2,3-trifluoro-5-(2-(4-(4-propylcyclohexyl)cyclohexyl) ethyl)benzene 5%

1,2,3-trifluoro-5-(2-(4-(4-pentylcyclohexyl)cyclohexyl) ethyl)benzene 5%

Example of Composition 5

4-(4-propylcyclohexyl)-1-(1,1-difluoropentyloxy)cyclohexane (CompoundNo. 96) 10%

4-(4-(1-butenyl)cyclohexyl)-1-(3-fluoropentyl)cyclohexane (Compound No.255) 10%

4-(4-propylcyclohexyl)-chlorobenzene 7%

4-(4-pentylcyclohexyl)-chlorobenzene 7%

4-(4-hexylcyclohexyl)-chlorobenzene 7%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-chlorobenzene 8%

4-(4-(4-propylcyclohexyl)cyclohexyl)-chlorobenzene 8%

4-(4-(4-pentylcyclohexyl)cyclohexyl)-chlorobenzene 8%

1-chloro-2-fluoro-4-(4-(2-(4-ethylcyclohexyl)ethyl) cyclohexyl)benzene7%

1-chloro-2-fluoro-4-(4-(2-(4-propylcyclohexyl)ethyl) cyclohexyl)benzene7%

1-chloro-2-fluoro-4-(4-(2-(4-pentylcyclohexyl)ethyl) cyclohexyl)benzene6%

1,2,3-trifluoro-5-(4-(4-propylcyclohexyl)cyclohexyl)benzene 8%

4'-(4-propylcyclohexyl)-3,4,5-trifluorobiphenyl 7%

Example of Composition 6

4-(4-propylcyclohexyl)-1-(methoxydifluoromethyl)cyclohexane (CompoundNo. 231) 5%

4-(4-butylcyclohexyl)-1-(2-methoxy-2, 2-difluoroethyl) cyclohexane(Compound No. 235) 5%

4'-ethyl-4-cyanobiphenyl 7%

4'-butyl-4-cyanobiphenyl 8%

4-(4-propylcyclohexyl)-cyanobenzene 10%

4-(4-pentylcyclohexyl)-cyanobenzene 10%

4-(4-methoxymethylcyclohexyl)-propylbenzene 10%

4-(4-methoxymethylcyclohexyl)-penty1benzene 10%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-methylbenzene 7%

4-(4-(4-propylcyclohexyl)cyclohexyl)-methylbenzene 8%

4-(4-(4-propylcyclohexyl)cyclohexyl)-cyanobenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-fluorobenzene 5%

4-(4-(4-pentylcyclohexyl)cyclohexyl)-fluorobenzene 5%

4-fluorophenyl-4-(4-propylcyclohexyl)benzoate 5%

Example of Composition 7

4-(4-(3-butenyl)cyclohexyl)-1-(3-fluoropropyl)cyclohexane (Compound No.256) 8%

4-(4-(2-propenyloxymethyl)cyclohexyl)-1-(3-fluoropropyl) cyclohexane(Compound No. 260) 8%

4-(4-(3-pentenyl)cyclohexyl)-1-(3-fluoropropyl)cyclohexane (Compound No.257) 9%

2-(3,4-difluorophenyl)-5-propylpyrimidine 5%

2-(3,4-difluorophenyl)-5-pentylpyrimidine 5%

4-(4-ethylcyclohexyl)-cyanobenzene 10%

4-(4-propylcyclohexyl)-cyanobenzene 10%

4-(4-ethylcyclohexyl)-3-fluoro-cyanobenzene 5%

4-(4-propylcyclohexyl)-3-fluoro-cyanobenzene 5%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-cyanobenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-cyanobenzene 5%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-3-fluoro-cyanobenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-3-fluoro-cyanobenzene 5%

2-(4'-fluorobiphenyl)-5-propylpyrimidine 5%

2-(4'-fluorobiphenyl)-5-butylpyrimidine 5%

4-(4-propylcyclohexyl)-ethoxybenzene 5%

Example of Composition 8

4-(4-pentylcyclohexyl)-(2-fluorobutyl)cyclohexane (Compound No. 60) 10%

4-(4-propylcyclohexyl)-1-(methoxydifluoromethyl)cyclohexane (CompoundNo. 231) 10%

4'-ethyl-4-cyanobiphenyl 5%

4-(4-methoxymethylcyclohexyl)-cyanobenzene 5%

4-(4-(2-ethoxyethoxy)cyclohexyl)-cyanobenzene 5%

4-(4-propylcyclohexyl)-cyanobenzene 10%

2-(4-ethylphenyl)-5-ethylpyrimidine 5%

2-(4-ethylphenyl)-5-propylpyrimidine 5%

2-(4-ethylphenyl)-5-butylpyrimidine 5%

2-(4-(4-propylcyclohexyl)phenyl)-5-ethylpyrimidine 5%

2-(4-(4-propylcyclohexyl)phenyl)-5-propylpyrimidine 5%

2-(4-(4-propylcyclohexyl)phenyl)-5-butylpyrimidine 5%

1,2-difluoro-4-(4-(4-ethylcyclohexyl)cyclohexyl)benzene 5%

1,2-difluoro-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene 5%

1,2-difluoro-4-(4-(4-pentylcyclohexyl)cyclohexyl)benzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-methoxybenzene 5%

4-(4-butylcyclohexyl)-propylcyclohexane 5%

Example of Composition 9

4-(4-propylcyclohexyl)-(1,1-difluorobutyl)cyclohexane (Compound No. 3)10%

4-(4-propylcyclohexyl)-(1,1-difluoropentyl)cyclohexane (Compound No. 4)10%

4-(4-(3-butenyl)cyclohexyl)-cyanobenzene 7%

4-(4-(3-pentenyl)cyclohexyl)-cyanobenzene 8%

4-(4-propylcyclohexyl)-cyanobenzene 5%

4-(2-(4-ethylphenyl)ethynyl)-methylbenzene 5%

4-(2-(4-methylphenyl)ethynyl)-hexylbenzene 10%

4-(2-(4-butylphenyl)ethynyl)-butylbenzene 5%

4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)-ethylbenzene 5%

4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)-propylbenzene 5%

4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethynyl)-ethylbenzene 5%

4-(2-(4-(2-(4-propylcyclohexyl)ethyl)phenyl)ethynyl)-propylbenzene 5%

2-(4'-fluorobiphenyl)-5-propylpyrimidine 5%

2-(4'-fluorobiphenyl)-5-butylpyrimidine 5%

4-(4-butylcyclohexyl)-propylcyclohexane 5%

4-fluorophenyl-4-(4-propylcyclohexyl)benzoate 5%

The composition mentioned above exhibits the values of physicalproperties as follows:

Clearing point:77.0° C., Δε:4.6, Δn:0.1637, viscosity:24.0 cP, thresholdvoltage at a cell thickness of 8.7 μ:2.32 V

Example of Composition 10

4-(4-pentylcyclohexyl)-(2,2-difluorobutyl)cyclohexane (Compound No. 14)10%

4-(4-(2-propenyloxymethyl)cyclohexyl)-1-(3-fluoropropyl) cyclohexane(Compound No. 260) 10%

4-(4-(3-pentenyl)cyclohexyl)-1-(3-fluoropropyl)cyclohexane (Compound No.257) 10%

2-(4-cyanophenyl)-5-propyldioxane 10%

4-cyanophenyl-4-propyl benzoate 10%

4-fluorophenyl-4-(4-propylcyclohexyl)cyclohexylcarboxylate 5%

4-fluorophenyl-4-(4-pentylcyclohexyl)cyclohexylcarboxylate 5%

4-(2-(4-ethylphenyl)ethynyl)-methoxybenzene 2.5%

4-(2-(4-propylphenyl)ethynyl)-methoxybenzene 2.5%

4-(2-(4-butylphenyl)ethynyl)-ethoxybenzene 2.5%

4-(2-(4-pentylphenyl)ethynyl)-methoxybenzene 2.5%

2-(4-ethoxyphenyl)-5-ethylpyrimidine 5%

2-(4-ethoxyphenyl)-5-propylpyrimidine 5%

4-butoxyphenyl-4-propylcyclohexylcarboxylate 5%

4-etoxycyclohexyl-4-butylcyclohexylcarboxylate 5%

2-fluoro-4- (4-propylcyclohexyl)-cyanobenzene 5%

2-fluoro-4-(4-(4-propylcyclohexyl)cyclohexyl)-cyanobenzene 5%

Example of Composition 11

4-(4-propylcyclohexyl)-(2,2-difluoropentoxy)cyclohexane (Compound No.98) 8%

4-(4-propylcyclohexyl)-(3,3-difluoropentoxy)cyclohexane (Compound No.100) 7%

4-(4-propylcyclohexyl)-methoxycyclohexane 7%

4-(4-propylcyclohexyl)-propoxycyclohexane 7%

4-(4-pentylcyclohexyl)-methoxycyclohexane 8%

4-(4-propylcyclohexyl)-fluorobenzene 8%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-trifluoromethoxybenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-difluoromethoxybenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-trifluoromethoxybenzene 5%

4-(4-(4-butylcyclohexyl)cyclohexyl)-trifluoromethoxybenzene 5%

4-(4-(4-pentylcyclohexyl)cyclohexyl)-trifluoromethoxybenzene 5%

4-(4-(4-pentylcyclohexyl)cyclohexyl)-difluoromethoxybenzene 5%

2,6-difluoro-4-(4-(4-propylcyclohexyl)cyclohexyl)-difluoromethoxybenzene 5%

2,6-difluoro-4-(4-(4-pentylcyclohexyl)cyclohexyl)-difluoromethoxybenzene 5%

1,2-difluoro-4-(2-(4-(4-propylcyclohexyl)cyclohexyl)ethyl) benzene 5%

1,2-difluoro-4-(2-(4-(4-pentylcyclohexyl)cyclohexyl)ethyl) benzene 5%

3,4-difluoro-4-(4-propylcyclohexyl)cyclohexylcarboxylate 5%

Example of Composition 12

4-(4-(4-propylcyclohexyl)cyclohexyl)-(2,2-difluoropentyl) cyclohexane10%

4-(4-(4-propylcyclohexyl)cyclohexyl)-(3,3-difluoropentyl) cyclohexane10%

4-(4-pentylcyclohexyl)-fluorobenzene 7%

4-(4-heptylcyclohexyl)-fluorobenzene 8%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-trifluoromethoxybenzene 7%

4-(4-(4-propylcyclohexyl)cyclohexyl)-trifluoromethoxybenzene 8%

4-(4-(4-butylcyclohexyl)cyclohexyl)-trifluoromethoxybenzene 7%

4-(4-(4-pentylcyclohexyl)cyclohexyl)-trifluoromethoxybenzene 8%4'-(4-propylcyclohexyl)-1,2-difluorobiphenyl 7%

4'-(4-pentylcyclohexyl)-1,2-difluorobiphenyl 8%

4-(2-(4-(4-propylcyclohexyl)cyclohexyl)ethyl)-trifluoromethoxybenzene 5%

4'-(4-pentylcyclohexyl)-2-fluoro-ethylbenzene 5%

2'-fluoro-4'-(4-propylcyclohexyl)-4-(4-propylcyclohexyl)biphenyl 5%

2'-fluoro-4'-(4-pentylcyclohexyl)-4-(4-propylcyclohexyl) biphenyl 5%

Example of Composition 13

4-(4-(3-butenyloxy)cyclohexyl)-(3-fluoropropyl)cyclohexane (Compound No.259) 7%

4-(4-(3-butenyl)cyclohexyl)-(2-fluoroethoxy)cyclohexane (Compound No.217) 8%

4-(4-(2-propenyl)cyclohexyl)-cyanobenzene 3%

4'-butyl-4-ethylbiphenyl 3%

4'-propyl-4-cyanobiphenyl 3%

2-fluoro-4-(4-ethylcyclohexyl)-cyanobenzene 3%

4-(2-(4-propylcyclohexyl)ethyl)-ethoxybenzene 3%

4'-pentyl-4-cyanobiphenyl 5%

4-cyanophenyl-4-propylbenzoate 5%

4-ethylphenyl-4-butylcyclohexylcarboxylate 10%

4-(2-(4-pentylcyclohexyl)ethyl)-ethoxybenzene 10%

4-methoxyphenyl-4-pentylcyclohexylcarboxylate 10%

4-propoxyphenyl-4-pentylcyclohexylcarboxylate 10%

2-(4-cyanophenyl)-5-(4-butylphenyl)pyrimidine 4%

4"-pentyl-4-cyanoterphenyl 4%

4-(2-(4-(4-pentylcyclohexyl)phenyl)ethyl)-butylbenzene 4%

2-(4-pentylphenyl)-5-(4-butylphenyl)pyrimidine 4%

4'-(4-pentylcyclohexyl)-4-(2-(4-propylcyclohexyl)ethyl) biphenyl 4%

Example of Composition 14

4-(4-(3-butenyl)cyclohexyl)-(3-fluoropropyl)cyclohexane (Compound No.256) 10%

4-(4-(1-(3-propenyloxy)methyl)cyclohexyl)-(3-fluoropropyl) cyclohexane(Compound No. 260) 10%

3,4-difluorophenyl-4-butylcyclohexylcarboxylate 5%

3,4-difluorophenyl-4-pentylcyclohexylcarboxylate 5%

3-fluoro-4-cyanophenyl-4-ethylbenzoate 5%

3-fluoro-4-cyanophenyl-4-propylbenzoate 5%

3-fluoro-4-cyanophenyl-4-butylbenzoate 5%

3-fluoro-4-cyanophenyl-4-penty1benzoate 5%

2-fluoro-4-(4-(3-methoxypropyl)cyclohexyl)-cyanobenzene 10%

3,4-difluorophenyl-4-(4-propylcyclohexyl) cyclohexylcarboxylate 5%

3,4-difluorophenyl-4-(4-pentylcyclohexyl) cyclohexylcarboxylate 5%

3-fluoro-4-cyanophenyl-4-(4-ethylcyclohexyl)benzoate 5%

3-fluoro-4-cyanophenyl-4-(4-propylcyclohexyl)benzoate 5%

3-fluoro-4-cyanophenyl-4-(4-butylcyclohexyl)benzoate 5%

3-fluoro-4-cyanophenyl-4-(4-pentylcyclohexyl)benzoate 5%

4-(2-(4-(4-propylcyclohexyl)phenyl)ethynyl)-ethylbenzene 10%

Example of Composition 15

4-(4-pentylcyclohexyl)-(2,2-difluorobutyl)cyclohexane (Compound No. 14)10%

4-(4-propylcyclohexyl)-(2-fluoropentyl)cyclohexane (Compound No. 52) 10%

1,2-difluoro-4-(2-(4-pentylcyclohexyl)ethyl)benzene 9%

1,2-difluoro-4-(4-(4-ethylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4-(4-(4-propylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4-(4-(4-pentylcyclohexyl)cyclohexyl)benzene 7%

1,2-difluoro-4'-(4-ethylcyclohexyl)biphenyl 5%

1,2-difluoro-4'-(4-propylcyclohexyl)biphenyl 5%

1,2-difluoro-4'-(4-pentylcyclohexyl)biphenyl 10%

4-fluorophenyl-4-pentylcyclohexylcarboxylate 7%

4-fluorophenyl-4-heptylcyclohexylcarboxylate 8%

4-(4-(4-propylcyclohexyl)cyclohexyl)-methylbenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-propylbenzene 5%

1-chloro-2-fluoro-4-(4-(2-(4-propylcyclohexyl)ethyl) cyclohexyl)benzene5%

The composition mentioned above exhibits the values of physicalproperties as follows:

Clearing point:75.8° C., Δε:2.9, Δn:0.0815, viscosity:19.1 cP, thresholdvoltage at a cell thickness of 8.8 μ:2.49 V

Example of Composition 16

4-(4-propylcyclohexyl)-1-(1,1-difluoroethyl)cyclohexane (Compound No. 1)10%

4-(4-propylcyclohexyl)-1-(1,1-difluoropropyl)cyclohexane (Compound No.2) 10%

4-(4-propylcyclohexyl)-chlorobenzene 7%

4-(4-pentylcyclohexyl)-chlorobenzene 7%

4-(4-hexylcyclohexyl)-chlorobenzene 7%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-chlorobenzene 8%

4-(4-(4-propylcyclohexyl)cyclohexyl)-chlorobenzene 8%

4-(4-(4-pentylcyclohexyl)cyclohexyl)-chlorobenzene 8%

1-chloro-2-fluoro-4-(4-(2-(4-ethylcyclohexyl)ethyl) cyclohexyl)benzene7%

1-chloro-2-fluoro-4-(4-(2-(4-propylcyclohexyl)ethyl) cyclohexyl)benzene7%

1-chloro-2-fluoro-4-(4-(2-(4-pentylcyclohexyl)ethyl) cyclohexyl)benzene6%

1,2,3-trifluoro-5-(4-(4-propylcyclohexyl)cyclohexyl)benzene 8%

4'-(4-propylcyclohexyl)-3,4,5-trifluorobiphenyl 7%

The composition mentioned above exhibits the values of physicalproperties as follows:

Clearing point:78.2° C., Δε:3.7, Δn:0.0883, viscosity:20.9 cP, thresholdvoltage at a cell thickness of 8.7 μ:2.41 V

Example of Composition 17

4-(4-pentylcyclohexyl)-1-(2-fluoroethyloxy)cyclohexane (Compound No.215) 5%

4-(2-(4-pentylcyclohexyl)ethyl)-1(2-fluoroethyloxy) cyclohexane(Compound No. 226) 5%

4'-ethyl-4-cyanobiphenyl 7%

4'-butyl-4-cyanobiphenyl 8%

4-(4-propylcyclohexyl)-cyanobenzene 10%

4-(4-pentylcyclohexyl)-cyanobenzene 10%

4-(4-methoxymethylcyclohexyl)-propylbenzene 10%

4-(4-methoxymethylcyclohexyl)-penty1benzene 10%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-methylbenzene 7%

4-(4-(4-propylcyclohexyl)cyclohexyl)-methylbenzene 8%

4-(4-(4-propylcyclohexyl)cyclohexyl)-cyanobenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-fluorobenzene 5%

4-(4-(4-pentylcyclohexyl)cyclohexyl)-fluorobenzene 5%

4-fluorophenyl-4-(4-propylcyclohexyl)benzoate 5%

The composition mentioned above exhibits the values of physicalproperties as follows:

Clearing point:79.7° C., Δε:6.5, An:0.1120, viscosity:19.2 cP, thresholdvoltage at a cell thickness of 8.8 μ: 2.02 V

Example of Composition 18

4-(4-(1-pentenyl)cyclohexyl)-1-(2-fluoroethyl)cyclohexane (Compound No.252) 10%

4-(4-(3-butenyl)cyclohexyl)-1-cyanobenzene 7%

4-(4-(3-pentenyl)cyclohexyl)-1-cyanobenzene 7%

4-(4-propylcyclohexyl)-1-cyanobenzene 16%

4-(4-propylcyclohexyl)-1-fluorobenzene 4%

4-(4-propylcyclohexyl)-1-ethyloxybenzene 9%

4-(2-(4-ethylphenyl)ethynyl)-1-methyloxybenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-1-methylbenzene 7%

4-(4-(4-propylcyclohexyl)cyclohexyl)-1-methyloxybenzene 4%

4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)-1- ethylbenzene 5%

4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)-1- propylbenzene 5%

4-(2-(2-fluoro-4-(4-propylcyclohexyl)phenyl)ethynyl)-1- butylbenzene 5%

4-(4-(4-ethylcyclohexyl)cyclohexyl)-1-cyanobenzene 5%

4-(4-(4-propylcyclohexyl)cyclohexyl)-1-cyanobenzene 5%

2-(4-(4-propylcyclohexyl)phenyl)-5-ethylpyrimidine 3%

2-(4-(4-propylcyclohexyl)phenyl)-5-propylpyrimidine 3%

The composition mentioned above exhibits the values of physicalproperties as follows:

Clearing point:99.5° C., Δε:7.0, Δn:0.1461, Viscosity:21.0 cP, Thresholdvoltage at a cell thickness of 8.7 μ:2.24V

The present invention will be explained below in more detail withreference to Examples. In the following Examples, all of the cyclohexanerings and double bonds in compounds belong to trans-form. Cr representscrystal, SB does smectic B phase, SX does unidentified smectic phase,and Iso represents isotropic liquid, and all phase transition points are1° C.

EXAMPLE 1

Production of 4-(4-pentylcyclohexyl)-(2,2-difluorobutyl) cyclohexane(Compound expressed by the fourmula (1) wherein R₁ is C₅ H₁₁, X is F, Yis H, Q and m are 0, n is 1, p is 2. (Compound No. 14))

First stage

A mixture of 50 g (0.17 mol) of 4-(4-pentylcyclohexyl) cyclohexyl aceticacid and 135 Ml of thionyl chloride was heated for 4 hours to reflux.Excess amount of thionyl chloride was separated under a reduced pressureto obtain 4-(4-pentylcyclohexyl)cyclohexyl acetic acid chloride.

On the other hand, a solution of 27.8 g (0.26 mol) of ethyl bromide in50 ml of THF was added dropwise to a mixture of 6.2 g (0.26 mol) ofmagnesium and 10 Ml of THF at a temperature of lower than 20° C. andthen stirred for 2 hours at a room temperature to obtain a THF solutionof ethylmagnesium bromide.

Dried toluene in an amount of 650 ml and 4.5 g (5% by weight of acidchloride) of Fe(acac)₃ were added to the4-(4-pentylcyclohexyl)cyclohexyl acetic acid chloride obtained in aprevious procedure and cooled down to -30° C. This solution was addeddropwise with the whole amount of the solution of ethyl magnesiumbromide obtained in a previous procedure at a temperature of lower than-30° C. and then stirred for 15 min at the same temperature. Thereaction product was put in 500 ml of 6N hydrochloric acid and thenextracted with 150 ml of toluene. The organic layer was washed with 6 Nhydrochloric acid once, with 2N aqueous solution of sodium hydroxidethrice, and with water twice, and then dried over anhydrous magnesiumsulfate. After the magnesium sulfate was separated, the solvent wasdistilled off under a reduced pressure, and the residue thus obtainedwas subjected to a silica gel column chromatography (eluate: toluene) toobtain 39.8 g of a crude4-(4-pentylcyclohexyl)-(2-oxyobutyl)cyclohexane. This product wasrecrystallized from 50 ml of ethanol to obtain 32.1 g (yield 62%) of4-(4-pentylcyclohexyl)-(2-oxobutyl)cyclohexane. Melting point:107.3°-107.4° C.

Second stage

A mixture of 10 g (33 mmol) of 4-(4-pentylcyclohexyl)-(2-oxobutyl)cyclohexane obtained in the first stage, 10.5 g (65 mmol) of DAST, and100 ml of THF was heated for 90 hours to reflux. The reaction productwas put in 100 ml of an ice water and then extracted with 100 ml oftoluene. The organic layer was washed with an aqueous solution saturatedwith potassium carbonate once and with a salt water thrice, and driedover anhydrous magnesium sulfate. After the magnesium sulfate wasseparated, the solvent was distilled off under a reduced pressure, andthe residue thus obtained was subjected to a silica gel columnchromatography (eluate: heptane) to obtain 1.58 g of a crude4-(4-pentylcyclohexyl)-(2,2-difluorobutyl) cyclohexane. This product wasrecrystallized from 30 ml of ethanol in a freezer to obtain 1.02 g(yield 10%) of 4-(4-pentylcyclohexyl)-(2,2-difluorobutyl)cyclohexane.Several kinds of spectra well supported its structure.

¹ H-NMR (TMS internal standard) δ (ppm): 0.69-2.06 (m)

GC-MS: 328 (M+)

Cr 2.3 SB 115.4 Iso (Unit is °C. The same is applied hereinafter.)

While the clearing point of the compound of the present invention was115.4° C. as mentioned above, it can be understood that the value ishigher compared with the clearing point of 104° C. of the knownbicyclohexane type compounds having the same structure except that thealkyl group at the end of molecule is not substituted with a fluorineatom (reference is made to Examined Japanese Patent Publication No.5-020418).

The following compounds (No. 1 through No. 46) were produced accordingto the method in Example 1. Each of the compounds are indicated byexcerpting parameters R₁, Q, and --(CH₂)_(n) CF₂ (CH₂)pH in thecompounds expressed by the general formula (1) (in the case of m=0, X=F,and Y=H in the group --(O)_(m) --(CH₂)_(n) --CFX--(CH₂)_(p) --Y of thegeneral formula (1)).

    ______________________________________                                                                               Phase                                  Comp-                                  tran-                                  ound                                   sition                                 No.   R.sub.1        I     --(CH.sub.2)nCF.sub.2 (CH.sub.2)PH                                                        point                                  ______________________________________                                        1     C.sub.3 H.sub.7                                                                              0     --CF.sub.2 CH.sub.3                                                                       Cr 5.1                                                                        SX 68.9                                                                       SB 77.1                                                                       Iso                                    2     C.sub.3 H.sub.7                                                                              0     --CH.sub.2 CF.sub.2 CH.sub.3                                                              Cr 23.0                                                                       SB 91.4                                                                       Iso                                    3     C.sub.3 H.sub.7                                                                              0     --CF.sub.2 (CH.sub.2).sub.3 H                                                             Cr 21.9                                                                       SB 8.8                                                                        Iso                                    4     C.sub.3 H.sub.7                                                                              0     --CF.sub.2 (CH.sub.2).sub.4 H                                                             Cr 35.3                                                                       SB 89.6                                                                       Iso                                    5     C.sub.3 H.sub.7                                                                              0     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             6     C.sub.3 H.sub.7                                                                              0     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.3 H                                                    Cr 22.1                                                                       SB                                                                            105.9                                                                         Iso                                    7     C.sub.3 H.sub.7                                                                              0     --(CH.sub.2).sub.2 CF.sub.2 (CH.sub.2).sub.2                                              Cr 17.5                                                                       SB                                                                            114.4                                                                         Iso                                    8     C.sub.3 H.sub.7                                                                              0     --(CH.sub.2).sub.3 CF.sub.2 (CH.sub.2).sub.2 H     9     C.sub.3 H.sub.7                                                                              0     --(CH.sub.2).sub.3 CF.sub.2 CH.sub.3               10    C.sub.4 H.sub.9                                                                              0     --CF.sub.2 (CH.sub.2).sub.4 H                      11    C.sub.4 H.sub.9                                                                              0     --(CH.sub.2).sub.3 CF.sub.2 CH.sub.3               12    C.sub.5 H.sub.11                                                                             0     --CF.sub.2 (CH.sub.2).sub.3 H                      13    C.sub.5 H.sub.11                                                                             0     --CF.sub.2 (CH.sub.2).sub.4 H                      14    C.sub.5 H.sub.11                                                                             0     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H                                                    Cr 2.3                                                                        SB                                                                            115.4                                                                         Iso                                    15    C.sub.5 H.sub.11                                                                             0     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.3 H             16    C.sub.5 H.sub.11                                                                             0     --(CH.sub.2).sub.2 CF.sub.2 CH.sub.3               17    C.sub.5 H.sub.11                                                                             0     --(CH.sub.2).sub.3 CF.sub.2 (CH.sub.2).sub.2 H     18    C.sub.5 H.sub.11                                                                             0     --(CH.sub.2).sub.3 CF.sub.2 CH.sub.3               19    C.sub.6 H.sub.13                                                                             0     --CF.sub.2 (CH.sub.2).sub.4 H                      20    C.sub.6 H.sub.13                                                                             0     --(CH.sub.2).sub.3 CF.sub.2 CH.sub.3               21    C.sub.3 H.sub.7 CH═CH--                                                                  0     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             22    CH.sub.3 CH═CH(CH.sub.2).sub.2 --                                                        0     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             23    CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             24    C.sub.2 H.sub.5                                                                              1     --CF.sub.2 (CH.sub.2).sub.2 H                      25    C.sub.2 H.sub.5                                                                              1     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             26    C.sub.3 H.sub.7                                                                              1     --CF.sub.2 (CH.sub.2).sub.3 H                      27    C.sub.3 H.sub.7                                                                              1     --CF.sub.2 (CH.sub.2).sub.4 H                      28    C.sub.3 H.sub.7                                                                              1     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             29    C.sub.3 H.sub.7                                                                              1     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.3 H             30    C.sub.3 H.sub.7                                                                              1     --(CH.sub.2).sub.2 CF.sub.2 CH.sub.3               31    C.sub.3 H.sub.7                                                                              1     --(CH.sub.2).sub.3 CF.sub.2 (CH.sub.2).sub.2 H     32    C.sub.3 H.sub.7                                                                              1     --(CH.sub.2).sub.3 CF.sub.2 CH.sub.3               33    C.sub.4 H.sub.9                                                                              1     --CF.sub.2 (CH.sub.2).sub.4 H                      34    C.sub.4 H.sub.9                                                                              1     --(CH.sub.2).sub.3 CF.sub.2 CH.sub.3               35    C.sub.5 H.sub.11                                                                             1     --CF.sub.2 (CH.sub.2).sub.2 H                                                             Cr27.5                                                                        SB89.2                                                                        Iso                                    36    C.sub.5 H.sub.11                                                                             1     --CF.sub.2 (CH.sub.2).sub.4 H                      37    C.sub.5 H.sub.11                                                                             1     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             38    C.sub.5 H.sub.11                                                                             1     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.3 H             39    C.sub.5 H.sub.11                                                                             1     --(CH.sub.2).sub.2 CF.sub.2 CH.sub.3               40    C.sub.5 H.sub.11                                                                             1     --(CH.sub.2).sub.3 CF.sub.2 (CH.sub.2).sub.2 H     41    C.sub.5 H.sub.11                                                                             1     --(CH.sub.2).sub.3 CF.sub.2 CH.sub.3               42    C.sub.6 H.sub.13                                                                             1     --CF.sub.2 (CH.sub.2).sub.4 H                      43    C.sub.6 H.sub.13                                                                             1     --(CH.sub.2).sub.3 CF.sub.2 CH.sub.3               44    C.sub.7 H.sub.15                                                                             1     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             45    C.sub.8 H.sub.17                                                                             1     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             46    C.sub.9 H.sub.19                                                                             1     --CH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H             ______________________________________                                    

Example 2

Production of 4-(4-pentylcyclohexyl)-(2-fluorobutyl) cyclohexane(Compound expressed by the formula (1) wherein R₁ is C₅ H₁₁, X and Y areH, Q and m are 0, n is 1, and p is 2. (Compound No. 60))

First Stage

While keeping inside of a reaction system at a temperature of lower than10° C., a solution of 5.0 g (16.3 mmol) of4-(4-pentylcyclohexyl)-(oxobutyl)cyclohexane obtained in Example 1 anddissolved in 35 ml of THF was added dropwise to a mixture of 0.46 g(12.2 mmol) of LAH and 2.5 ml of THF and further stirred for 5 hours ata room temperature. Under cooled condition, 5 ml of ethyl acetate andthen 100 ml of 6N hydrochloric acid were added to terminate thereaction. After extracted with 50 ml of ethyl acetate, the organic layerwas washed with water twice and dried over anhydrous magnesium sulfate.After the magnesium sulfate was separated, the solvent was distilled offunder a reduced pressure, and the residue thus obtained wasrecrystallized from 8 ml of hexane to obtain 5.0 g (yield 99%) of4-(4-pentylcyclohexyl)-(2-hydroxybutyl)cyclohexane. Melting point:130.9°-131.1° C.

Second stage

A mixture of 3.32 g (10.8 mmol) of4-(4-pentylcyclohexyl)-(2-hydorxybutyl)cyclohexane obtained in the firststage, 2.6 g (16.2 mmol) of DAST, and 30 ml of dichloromethane wasstirred for 2 hours at a temperature of lower than 10° C. The reactionproduct was put in 50 ml of an ice water and then extracted with 50 mlof toluene. The organic layer was washed with an aqueous solutionsaturated with sodium hydrogencarbonate once and with water twice, anddried over anhydrous magnesium sulfate. After the magnesium sulfate wasseparated, the solvent was distilled off under a reduced pressure, andthe residue thus obtained was subjected to a silica gel columnchromatography (eluate: heptane) to obtain 1.3 g of a crude4-(4-pentylcyclohexyl)-(2-fluorobutyl)cyclohexane. This product wasrecrystallized twice from a mixed solvent of 8 nQ of ethanol and 2 ml ofbenzene in a freezer to obtain 0.81 g (yield 24%) of4-(4-pentylcyclohexyl)-(2-fluorobutyl)cyclohexane. Several kinds ofspectra well supported its structure.

¹ H-NMR (TMS internal standard) δ (ppm): 4.51 (dm, 1H), 1.83-0.81 (m,38H)

GC-MS: 310 (M+)

Cr 10.4 SB 119.9 Iso

It can be understood that the clearing point 119.9° C. mentioned aboveis considerably higher compared with the clearing point of 104° C. ofthe known bicyclohexane type compound having the same structure exceptthat the alkyl group at the end of molecule is not substituted with afluorine atom (reference is made to Examined Japanese Patent PublicationNo. 5-020418).

The following compounds (No. 47 through No. 92) were produced accordingto the method in Example 2. Each of the compounds are indicated byexcerpting parameters R₁, Q, and --(CH₂)_(n) CFH(CH₂)_(p) H in the sameway as described before.

    ______________________________________                                                                                Phase                                 Com-                                    tran-                                 pound                                   sition                                No.   R.sub.1        I     --(CH.sub.2)nCFH(CH.sub.2)pH                                                               point                                 ______________________________________                                        47    C.sub.2 H.sub.5                                                                              0     --CFH(CH.sub.2).sub.2 H                            48    C.sub.2 H.sub.5                                                                              0     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   49    C.sub.3 H.sub.7                                                                              0     --CFH(CH.sub.2).sub.3 H                            50    C.sub.3 H.sub.7                                                                              0     --CFH(CH.sub.2).sub.4 H                            51    C.sub.3 H.sub.7                                                                              0     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   52    C.sub.3 H.sub.7                                                                              0     --CH.sub.2 CFH(CH.sub.2).sub.3 H                                                           Cr                                                                            41.5                                                                          SB                                                                            110.2                                                                         Iso                                   53    C.sub.3 H.sub.7                                                                              0     --(CH.sub.2).sub.2 CFHCH.sub.3                                                             Cr                                                                            33.5                                                                          SB                                                                            107.1                                                                         Iso                                   54    C.sub.3 H.sub.7                                                                              0     --(CH.sub.2).sub.3 CFH(CH.sub.2).sub.2 H           55    C.sub.3 H.sub.7                                                                              0     --(CH.sub.2).sub.3 CFHCH.sub.3                     56    C.sub.4 H.sub.9                                                                              0     --CFH(CH.sub.2).sub.4 H                            57    C.sub.4 H.sub.9                                                                              0     --(CH.sub.2).sub.3 CFHCH.sub.3                     58    C.sub.5 H.sub.11                                                                             0     --CFH(CH.sub.2).sub.3 H                            59    C.sub.5 H.sub.11                                                                             0     --CFH(CH.sub.2).sub.4 H                            60    C.sub.5 H.sub.11                                                                             0     --CH.sub.2 CFH(CH.sub.2).sub.2 H                                                           Cr                                                                            10.4                                                                          SB                                                                            119.9                                                                         Iso                                   61    C.sub.5 H.sub.11                                                                             0     --CH.sub.2 CFH(CH.sub.2).sub.3 H                   62    C.sub.5 H.sub.11                                                                             0     --(CH.sub.2).sub.2 CFHCH.sub.3                     63    C.sub.5 H.sub.11                                                                             0     --(CH.sub.2).sub.3 CFH(CH.sub.2).sub.2 H           64    C.sub.5 H.sub.11                                                                             0     --(CH.sub.2).sub.3 CFHCH.sub.3                     65    C.sub.6 H.sub.13                                                                             0     --CFH(CH.sub.2).sub.4 H                            66    C.sub.6 H.sub.13                                                                             0     --(CH.sub.2).sub.3 CFHCH.sub.3                     67    C.sub.3 H.sub.7 CH═CH--                                                                  0     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   68    CH.sub.3 CH═CH(CH.sub.2).sub.2 --                                                        0     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   69    CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   70    C.sub.2 H.sub.5                                                                              1     --CFH(CH.sub.2).sub.2 H                            71    C.sub.2 H.sub.5                                                                              1     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   72    C.sub.3 H.sub.7                                                                              1     --CFH(CH.sub.2).sub.3 H                            73    C.sub.3 H.sub.7                                                                              1     --CFH(CH.sub.2).sub.4 H                            74    C.sub.3 H.sub.7                                                                              1     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   75    C.sub.3 H.sub.7                                                                              1     --CH.sub.2 CFH(CH.sub.2).sub.3 H                   76    C.sub.3 H.sub.7                                                                              1     --(CH.sub.2).sub.2 CFHCH.sub.3                     77    C.sub.3 H.sub.7                                                                              1     --(CH.sub.2).sub.3 CFH(CH.sub.2).sub.2 H           78    C.sub.3 H.sub.7                                                                              1     --(CH.sub.2).sub.3 CFHCH.sub.3                     79    C.sub.4 H.sub.9                                                                              1     --CFH(CH.sub.2).sub.4 H                            80    C.sub.4 H.sub.9                                                                              1     --(CH.sub.2).sub.3 CFHCH.sub.3                     81    C.sub.5 H.sub.11                                                                             1     --CFH(CH.sub.2).sub.3 H                            82    C.sub.5 H.sub.11                                                                             1     --CFH(CH.sub.2).sub.4 H                            83    C.sub.5 H.sub.11                                                                             1     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   84    C.sub.5 H.sub.11                                                                             1     --CH.sub.2 CFH(CH.sub.2).sub.3 H                   85    C.sub.5 H.sub.11                                                                             1     --(CH.sub.2).sub.2 CFHCH.sub.3                     86    C.sub.5 H.sub.11                                                                             1     --(CH.sub.2).sub.3 CFH(CH.sub.2).sub.2 H           87    C.sub.5 H.sub.11                                                                             1     --(CH.sub.2).sub.3 CFHCH.sub.3                     88    C.sub.6 H.sub.13                                                                             1     --CFH(CH.sub.2).sub.4 H                            89    C.sub.6 H.sub.13                                                                             1     --(CH.sub.2).sub.3 CFHCH.sub.3                     90    C.sub.7 H.sub.15                                                                             1     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   91    C.sub.8 H.sub.17                                                                             1     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   92    C.sub.9 H.sub.19                                                                             1     --CH.sub.2 CFH(CH.sub.2).sub.2 H                   ______________________________________                                    

EXAMPLE 3

Production of 4-(4-pentylcyclohexyl)-(2,2-difluorobutyloxy) cyclohexane(Compound expressed by the formula (1) wherein R₁ is C₅ H₁₁, X is F, Yis H, Q is 0, m and n are 1, and p is 2. (Compound No. 106))

First Stage

A solution of 25.2 g (0.1 mol) of 4-(4-pentylcyclohexyl) cyclohexanol in50 ml of THF was added dropwise to a mixture of 5.2 g (0.11 mol) ofsodium hydride and 20 ml of THF at a temperature of lower than 10° C.Then, 50 ml of DMF was further added and stirred for 1 hour at a roomtemperature. While keeping inside of the reaction system at atemperature of lower than 0°C., a solution of 21 g (0.1 mol) of2-bromomethyl-2-ethyl-1,3-dioxane derived from commercially available1-bromo-2-butanone in 50 ml of THF was added dropwise, and stirred for 2hours at a room temperature and then for 2 hours at 50° C. This solutionwas added with 50 ml of 6N hydrochloric acid, stirred for 1 hour at 50°C., added with 200 ml of toluene, and extracted. The organic layer waswashed once with an aqueous solution saturated with potassium carbonateand twice with water, and dried over anhydrous magnesium sulfate. Afterthe anhydrous magnesium sulfate was separated, the solvent was distilledoff under a reduced pressure, and the residue thus obtained wassubjected to a silica gel column chromatography (eluate: toluene) toobtain 20.9 g (yield 65%) of4-(4-pentylcyclohexyl)-(2-oxobutyloxy)cyclohexane.

Second stage

A mixture of 9.7 g (0.03 mol) of4-(4-pentylcyclohexyl)-(2-orxobutyloxy)cyclohexane obtained in the firststage, 9.7 g (0.06 mol) of DAST, and 100 ml of THF was heated for 80hours to reflux. The reaction product was put in 100 ml of an ice waterand then extracted with 100 ml of toluene. The organic layer was washedwith an aqueous solution saturated with potassium carbonate once andwith a salt water five times, and dried over anhydrous magnesiumsulfate. After the magnesium sulfate was separated, the solvent wasdistilled off under a reduced pressure, and the residue thus obtainedwas subjected to a silica gel column chromatography (eluate: heptane),and recrystallized from 45 ml of ethanol in a freezer to obtain 1.65 g(yield 16%) of 4-(4-pentylcyclohexyl)-(2,2-difluorobutyloxy)cyclohexane. Several kinds of spectra well supported its structure.

The following compounds (No. 93 through No. 138) were produced accordingto the method in Example 3.Each of the compounds are indicated byexcerpting parameters R₁, Q, and --O(CH₂)_(n) CF₂ (CH₂)_(p) H in thesame way as described before.

    ______________________________________                                        Compound No.                                                                           R.sub.1        I     --O(CH.sub.2)nCF.sub.2 (CH.sub.2)pH             ______________________________________                                         93      C.sub.2 H.sub.5                                                                              0     --OCF.sub.2 (CH.sub.2).sub.2 H                   94      C.sub.2 H.sub.5                                                                              0     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H          95      C.sub.3 H.sub.7                                                                              0     --OCF.sub.2 (CH.sub.2).sub.3 H                   96      C.sub.3 H.sub.7                                                                              0     --OCF.sub.2 (CH.sub.2).sub.4 H                   97      C.sub.3 H.sub.7                                                                              0     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H          98      C.sub.3 H.sub.7                                                                              0     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.3 H          99      C.sub.3 H.sub.7                                                                              0     --O(CH.sub.2).sub.2 CF.sub.2 CH.sub.3           100      C.sub.3 H.sub.7                                                                              0     --O(CH.sub.2).sub.2 CF.sub.2 (CH.sub.2).sub.                                  2 H                                             101      C.sub.3 H.sub.7                                                                              0     --O(CH.sub.2).sub.3 CF.sub.2 CH.sub.3           102      C.sub.4 H.sub.9                                                                              0     --OCF.sub.2 (CH.sub.2).sub.4 H                  103      C.sub.4 H.sub.9                                                                              0     --O(CH.sub.2).sub.3 CF.sub.2 CH.sub.3           104      C.sub.5 H.sub.11                                                                             0     --OCF.sub.2 (CH.sub.2).sub.3 H                  105      C.sub.5 H.sub.11                                                                             0     --OCF.sub.2 (CH.sub.2).sub.4 H                  106      C.sub.5 H.sub.11                                                                             0     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H         107      C.sub.5 H.sub.11                                                                             0     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.3 H         108      C.sub.5 H.sub.11                                                                             0     --O(CH.sub.2).sub.2 CF.sub.2 CH.sub.3           109      C.sub.5 H.sub.11                                                                             0     --O(CH.sub.2).sub.3 CF.sub.2 (CH.sub.2).sub.                                  2 H                                             110      C.sub.5 H.sub.11                                                                             0     --O(CH.sub.2).sub.3 CF.sub.2 CH.sub.3           111      C.sub.6 H.sub.13                                                                             0     --OCF.sub.2 (CH.sub.2).sub.4 H                  112      C.sub.6 H.sub.13                                                                             0     --O(CH.sub.2).sub.3 CF.sub.2 CH.sub.3           113      C.sub.3 H.sub.7 CH═CH--                                                                  0     --OCF.sub.2 (CH.sub.2).sub.3 H                  114      C.sub.3 H.sub.7 CH═CH--                                                                  0     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H         115      CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --OCF.sub.2 (CH.sub.2).sub.3 H                  116      C.sub.2 H.sub.5                                                                              1     --OCF.sub.2 (CH.sub.2).sub.2 H                  117      C.sub.2 H.sub.5                                                                              1     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H         118      C.sub.3 H.sub.7                                                                              1     --OCF.sub.2 (CH.sub.2).sub.3 H                  119      C.sub.3 H.sub.7                                                                              1     --OCF.sub.2 (CH.sub.2).sub.4 H                  120      C.sub.3 H.sub.7                                                                              1     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H         121      C.sub.3 H.sub.7                                                                              1     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.3 H         122      C.sub.3 H.sub.7                                                                              1     --O(CH.sub.2).sub.2 CF.sub.2 CH.sub.3           123      C.sub.3 H.sub.7                                                                              1     --O(CH.sub.2).sub.3 CF.sub.2 (CH.sub.2).sub.                                  2 H                                             124      C.sub.3 H.sub.7                                                                              1     --O(CH.sub.2).sub.3 CF.sub.2 CH.sub.3           125      C.sub.4 H.sub.9                                                                              1     --OCF.sub.2 (CH.sub.2).sub.4 H                  126      C.sub.4 H.sub.9                                                                              1     --O(CH.sub.2).sub.3 CF.sub.2 CH.sub.3           127      C.sub.5 H.sub.11                                                                             1     --OCF.sub.2 (CH.sub.2).sub.3 H                  128      C.sub.5 H.sub.11                                                                             1     --OCF.sub.2 (CH.sub.2).sub.4 H                  129      C.sub.5 H.sub.11                                                                             1     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H         130      C.sub.5 H.sub.11                                                                             1     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.3 H         131      C.sub.5 H.sub.11                                                                             1     --O(CH.sub.2).sub.2 CF.sub.2 CH.sub.3           132      C.sub.5 H.sub.11                                                                             1     --O(CH.sub.2).sub.3 CF.sub.2 (CH.sub.2).sub.                                  2 H                                             133      C.sub.5 H.sub.11                                                                             1     --O(CH.sub.2).sub.3 CF.sub.2 CH.sub.3           134      C.sub.6 H.sub.13                                                                             1     --OCF.sub.2 (CH.sub.2).sub.4 H                  135      C.sub.6 H.sub.13                                                                             1     --O(CH.sub.2).sub.3 CF.sub.2 CH.sub.3           136      C.sub.7 H.sub.15                                                                             1     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H         137      C.sub.8 H.sub.17                                                                             1     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2 H         138      C.sub.9 H.sub.19                                                                             1     --OCH.sub.2 CF.sub.2 (CH.sub.2).sub.2           ______________________________________                                                                      H                                           

EXAMPLE 4

Production of 4-(4-propylcyclohexyl)-(3,3-difluoropropyloxy)cyclohexane(Compound expressed by the formula (1) wherein R₁ is C₃ H₇, X is F, Y isH, Q is 0, m is 1, n is 2, and p is 0.(Compound No. 141))

First Stage

A mixture of 94.3 g (0.42 mol) of 4-(4-propylcyclohexyl) cyclohexanone,64.5 g (0.85 mol) of 1,3-propanediol, 2 ml of concentrated hydrochloricacid, and 200 ml of toluene was heated while stirring to reflux for 3hours while separating produced water by Dean and Stark method. Theproduct was put in 500 ml of an aqueous solution saturated with sodiumhydrogencarbonate, and the organic layer separated was washed with watertwice and dried over anhydrous magnesium sulfate. After the magnesiumsulfate was separated, the solvent was distilled off under a reducedpressure and the residue was recrystallized from 100 ml of ethanol toobtain 72.1 g (yield 61%) of 4-(4-propylcyclohexyl)cyclohexanonespiroketal body. Melting point: 52.6°-53.7° C.

Second stage

A suspension of 2.85 g (0.075 mol) of LAH in 80 ml of anhydrous diethylether was added dropwise to a solution of 38.4 g (0.14 mol) of anhydrousaluminum chloride in 80 ml of anhydrous diethyl ether and stirred for 30min. To this solution was added dropwise a solution of 40 g (0.14 mol)of the spiroketal body obtained in the first stage and dissolved in 80ml of anhydrous diethyl ether, and heated for 3 hours to reflux. Then,under cooling with ice, 20 ml of water was added to destroy an excessamount of the reducing agent and then put in 200 ml of an ice water. Itwas extracted twice with 400 ml of ethyl acetate, and the organic layerwas washed with water twice and dried over anhydrous magnesium sulfate.After the magnesium sulfate was separated, the solvent was distilled offunder a reduced pressure, and the residue was recrystallized twice from40 ml of heptane to obtain 20.7 g (yield 51%) of4-(4-propylcyclohexyl)-(3-hydroxypropyloxy)cyclohexane. Melting point:110.4°-111.0° C.

Third stage

DMSO in an amount of 2.13 ml (0.03 mol) was added dropwise to a mixtureof 1.74 ml (0.02 mol) of oxalic acid chloride and 40 ml ofdichloromethane at -50° C. and stirred for 10 min. While keeping insideof the reaction system at -60°C., this solution was added dropwise witha solution of 2.82 g (0.01 mol) of the4-(4-propylcyclohexyl)-(3-hydroxypropyloxy)cyclohexane obtained in thesecond stage and dissolved in 20 ml of dichloromethane and stirred for 1hour. To this solution was added 14 ml of triethylamine, temperature ofthe solution was returned to a room temperature, stirred for 15 min, andthe solution was added with 80 ml of an aqueous solution saturated withammonium chloride. The organic layer was separated and dried overanhydrous magnesium sulfate. After the magnesium sulfate was separated,the solvent was distilled off under a reduced pressure, and the residuewas subjected to a silica gel column chromatography (eluate:toluene/ethylacetate (9/1)) to obtain 1.93 g of a crude4-(4-propylcyclohexyl)-(3-oxopropyoxy) cyclohexane. This product wasrecrystallized from 12 ml of ethanol to obtain 1.3 g (yield 46%) of4-(4-propylcyclohexyl)-(3-oxopropyloxy)cyclohexane.

Fourth stage

A mixture of 1.3 g (4.6 mmol) of4-(4-propylcyclohexyl)-(3-oxopropyloxy)cyclohexane obtained in the thirdstage, 2.0 g (12 mmol) of DAST, and 5 ml of dichloromethane was stirredovernight at a room temperature. The product was put in 20 ml of an icewater and extracted with 20 ml of toluene. The organic layer was washedonce with an aqueous solution saturated with potassium carbonate andthen twice with water, and dried over anhydrous magnesium sulfate. Afterthe magnesium sulfate was separated, the solvent was distilled off undera reduced pressure, and the residue thus obtained was subjected to asilica gel column chromatography (eluate: toluene) to obtain 0.78 g of acrude 4-(4-propylcyclohexyl)-(3,3-difluoropropyloxy)cyclohexane. Thisproduct was recrystallized from 3.5 ml of ethanol in a freezer to obtain0.51 g (yield 17%) of4-(4-propylcyclohexyl)-(3,3-difluoropropyloxy)cyclohexane. Several kindsof spectra well supported its structure.

¹ H-NMR (TMS internal standard) δ (ppm): 5.91 (tt, 1H), 3.56 (t, 2H),3.05 (m, 1H), 2.31-0.76 (m, 28H)

GC-MS: 302 (M+)

Cr 24.3 SB 53.5 Iso

The following compounds (No. 139 through No. 160) were producedaccording to the method in Example 4.Each of the compounds are indicatedby excerpting parameters R₁, Q, and --O(CH₂)_(n) CF₂ H in the same wayas described before.

    ______________________________________                                        Com-                                Phase                                     pound                               transition                                No.   R.sub.1       I     --O(CH.sub.2)nCF.sub.2 H                                                                point                                     ______________________________________                                        139   C.sub.2 H.sub.5                                                                             0     --O(CH.sub.2).sub.2 CF.sub.2 H                      140   C.sub.2 H.sub.5                                                                             0     --O(CH.sub.2).sub.3 CF.sub.2 H                      141   C.sub.3 H.sub.7                                                                             0     --O(CH.sub.2).sub.2 CF.sub.2 H                                                          Cr24.3                                                                        SB 53.5 Iso                               142   C.sub.3 H.sub.7                                                                             0     --O(CH.sub.2).sub.3 CF.sub.2 H                      143   C.sub.3 H.sub.7                                                                             0     --O(CH.sub.2).sub.4 CF.sub.2 H                      144   C.sub.4 H.sub.9                                                                             0     --O(CH.sub.2).sub.2 CF.sub.2 H                      145   C.sub.4 H.sub.9                                                                             0     --O(CH.sub.2).sub.4 CF.sub.2 H                      146   C.sub.5 H.sub.11                                                                            0     --O(CH.sub.2).sub.2 CF.sub.2 H                      147   C.sub.5 H.sub.11                                                                            0     --O(CH.sub.2).sub.3 CF.sub.2 H                      148   C.sub.5 H.sub.11                                                                            0     --O(CH.sub.2).sub.4 CF.sub.2 H                      149   CH.sub.3 CH═CH(CH.sub.2).sub.2 --                                                       0     --O(CH.sub.2).sub.3 CF.sub.2 H                      150   C.sub.2 H.sub.5                                                                             1     --O(CH.sub.2).sub.2 CF.sub.2 H                      151   C.sub.2 H.sub.5                                                                             1     --O(CH.sub.2).sub.3 CF.sub.2 H                      152   C.sub.3 H.sub.7                                                                             1     --O(CH.sub.2).sub.2 CF.sub.2 H                      153   C.sub.3 H.sub.7                                                                             1     --O(CH.sub.2).sub.3 CF.sub.2 H                      154   C.sub.3 H.sub.7                                                                             1     --O(CH.sub.2).sub.4 CF.sub.2 H                      155   C.sub.4 H.sub.9                                                                             1     --O(CH.sub.2).sub.2 CF.sub.2 H                      156   C.sub.4 H.sub.9                                                                             1     --O(CH.sub.2).sub.4 CF.sub.2 H                      157   C.sub.5 H.sub.11                                                                            1     --O(CH.sub.2).sub.2 CF.sub.2 H                      158   C.sub.5 H.sub.11                                                                            1     --O(CH.sub.2).sub.3 CF.sub.2 H                      159   C.sub.5 H.sub.11                                                                            1     --O(CH.sub.2).sub.4 CF.sub.2 H                      160   C.sub.3 H.sub.7 CH═CH--                                                                 1     --O(CH.sub.2).sub.3 CF.sub.2 H                      ______________________________________                                    

EXAMPLE 5

Production of 4-(4-pentylcyclohexyl)-(2-fluorobutyloxy) cyclohexane(Compound expressed by the formula (1) wherein R₁ is C₅ H₁₁, X and Y areH, Q is 0, m and n are 1, and p is 2. Compound No. 174))

First Stage

While keeping inside of a reaction system at a temperature of lower than10° C., a solution of 5.24 g (16.3 mmol) of4-(4-pentylcyclohexyl)-(2-oxobutyloxy)cyclohexane produced in Example 3and dissolved in 35 ml of THF was added dropwise to a mixture of 0.46 g(12.2 mmol) of LAH and 2.5 ml of THF and further stirred for 5 hours ata room temperature. To this solution, under cooling, were added 5 ml ofethylacetate and then 10 ml of 2N aqueous solution of sodium hydroxideto terminate the reaction. After undissolved products were separated,the solvent was distilled off under a reduced pressure and the residuethus obtained was recrystallized from 15 ml of hexane to obtain 5.0 g(yield 95%) of 4-(4-pentylcyclohexyl)-(2-hydroxybutyloxy)cyclohexane.

Second stage

A mixture of 3.34 g (10 mmol) of4-(4-pentylcyclohexyl)-(2-hydroxybutyloxy)cyclohexane obtained in thefirst stage, 1.61 g (10 mmol) of DAST, and 30 ml of dichloromethane wasstirred for 2 hours at a temperature of lower than 10° C. The reactionproduct was put in 50 ml of an ice water and then extracted with 50 mlof toluene. The organic layer was washed once with an aqueous solutionsaturated with sodium hydrogencarbonate and twice with water, and driedover anhydrous magnesium sulfate. After the magnesium sulfate wasseparated, the solvent was distilled off under a reduced pressure, andthe residue thus obtained was subjected to a silica gel columnchromatography (eluate: heptane) to obtain a crude product of4-(4-pentylcyclohexyl)-(2-fluorobutyloxy)cyclohexane. This product wasrecrystallized from a mixed solvent of 10 ml of ethanol and 3 ml ofbenzene in a freezer to obtain 0.64 g (yield 20%) of4-(4-pentylcyclohexyl)-(2-fluorobutyloxy)cyclohexane. Several kinds ofspectra well supported its structure.

The following compounds (No. 161 through No. 207) were producedaccording to the method in Example 5.Each of the compounds are indicatedby excerpting parameters R₁, Q, and --O(CH₂)_(n) CFH(CH₂)_(p) H in thesame way as described before.

    ______________________________________                                        Compound No.                                                                           R.sub.1        I     --O(CH.sub.2)nCFH(CH.sub.2)pH                   ______________________________________                                        161      C.sub.2 H.sub.5                                                                              0     --OCFH(CH.sub.2).sub.2 H                        162      C.sub.2 H.sub.5                                                                              0     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               163      C.sub.3 H.sub.7                                                                              0     --OCFH(CH.sub.2).sub.3 H                        164      C.sub.3 H.sub.7                                                                              0     --OCFH(CH.sub.2).sub.4 H                        165      C.sub.3 H.sub.7                                                                              0     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               166      C.sub.3 H.sub.7                                                                              0     --OCH.sub.2 CFH(CH.sub.2).sub.3 H               167      C.sub.3 H.sub.7                                                                              0     --O(CH.sub.2).sub.2 CFHCH.sub.3                 168      C.sub.3 H.sub.7                                                                              0     --O(CH.sub.2).sub.3 CFH(CH.sub.2).sub.2 H       169      C.sub.3 H.sub.7                                                                              0     --O(CH.sub.2).sub.3 CFHCH.sub.3                 170      C.sub.4 H.sub.9                                                                              0     --OCFH(CH.sub.2).sub.4 H                        171      C.sub.4 H.sub.9                                                                              0     --O(CH.sub.2).sub.3 CFHCH.sub.3                 172      C.sub.5 H.sub.11                                                                             0     --OCFH(CH.sub.2).sub.3 H                        173      C.sub.5 H.sub.11                                                                             0     --OCFH(CH.sub.2).sub.4 H                        174      C.sub.5 H.sub.11                                                                             0     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               175      C.sub.5 H.sub.11                                                                             0     --OCH.sub.2 CFH(CH.sub.2).sub.3 H               176      C.sub.5 H.sub.11                                                                             0     --O(CH.sub.2).sub.2 CFHCH.sub.3                 177      C.sub.5 H.sub.11                                                                             0     --O(CH.sub.2).sub.3 CFH(CH.sub.2).sub.2 H       178      C.sub.5 H.sub.11                                                                             0     --O(CH.sub.2).sub.3 CFHCH.sub.3                 179      C.sub.6 H.sub.13                                                                             0     --OCFH(CH.sub.2).sub.4 H                        180      C.sub.6 H.sub.13                                                                             0     --O(CH.sub.2).sub.3 CFHCH.sub.3                 181      C.sub.3 H.sub.7 CH═CH--                                                                  0     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               182      CH.sub.3 CH═CH(CH.sub.2).sub.2 --                                                        0     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               183      CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               184      CH.sub.3       1     --O(CH.sub.2).sub.2 CFH(CH.sub.2).sub.2 H       185      C.sub.2 H.sub.5                                                                              1     --OCFH(CH.sub.2).sub.2 H                        186      C.sub.2 H.sub.5                                                                              1     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               187      C.sub.3 H.sub.7                                                                              1     --OCFH(CH.sub.2).sub.3 H                        188      C.sub.3 H.sub.7                                                                              1     --OCFH(CH.sub.2).sub.4 H                        189      C.sub.3 H.sub.7                                                                              1     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               190      C.sub.3 H.sub.7                                                                              1     --OCH.sub.2 CFH(CH.sub.2).sub.3 H               191      C.sub.3 H.sub.7                                                                              1     --O(CH.sub.2).sub.2 CFHCH.sub.3                 192      C.sub.3 H.sub.7                                                                              1     --O(CH.sub.2).sub.3 CFH(CH.sub.2).sub.2 H       193      C.sub.3 H.sub.7                                                                              1     --O(CH.sub.2).sub.3 CFHCH.sub.3                 194      C.sub.4 H.sub.9                                                                              1     --OCFH(CH.sub.2).sub.4 H                        195      C.sub.4 H.sub.9                                                                              1     --O(CH.sub.2).sub.3 CFHCH.sub.3                 196      C.sub.5 H.sub.11                                                                             1     --OCFH(CH.sub.2).sub.3 H                        197      C.sub.5 H.sub.11                                                                             1     --OCFH(CH.sub.2).sub.4 H                        198      C.sub.5 H.sub.11                                                                             1     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               199      C.sub.5 H.sub.11                                                                             1     --OCH.sub.2 CFH(CH.sub.2).sub.3 H               200      C.sub.5 H.sub.11                                                                             1     --O(CH.sub.2).sub.2 CFHCH.sub.3                 201      C.sub.5 H.sub.11                                                                             1     --O(CH.sub.2).sub.3 CFH(CH.sub.2).sub.2 H       202      C.sub.5 H.sub.11                                                                             1     --O(CH.sub.2).sub.3 CFHCH.sub.3                 203      C.sub.6 H.sub.13                                                                             1     --OCFH(CH.sub.2).sub.4 H                        204      C.sub.6 H.sub.13                                                                             1     --O(CH.sub.2).sub.3 CFHCH.sub.3                 205      C.sub.7 H.sub.15                                                                             1     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               206      C.sub.8 H.sub.17                                                                             1     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               207      C.sub.9 H.sub.19                                                                             1     --OCH.sub.2 CFH(CH.sub.2).sub.2 H               ______________________________________                                    

EXAMPLE 6

Production of 4-(4-propylcyclohexyl)-(3-fluoropropyloxy) cyclohexane(Compound expressed by the formula (1) wherein R₁ is C₃ H₇, X and Y areH, Q is 0, m is 1, n is 2, and p is 0. Compound No. 211))

First Stage

A mixture of 2.75 g (9.8 mmol) of4-(4-propylcyclohexyl)-(3-hydroxypropyloxy)cyclohexane obtained inExample 4, 3.14 g (19.6 mmol) of DAST, and 25 ml of dichloromethane wasstirred for 5 hours at a room temperature. The reaction product was putin 40 ml of an ice water and extracted with 40 ml of toluene. Theorganic layer was washed with water twice and dried over anhydrousmagnesium sulfate. The magnesium sulfate was separated, the solvent wasdistilled off under a reduced pressure, and the residue thus obtainedwas subjected to a silica gel column chromatography (eluate: toluene) toobtain 1.87 g of a crude 4-(4-propylcyclohexyl)-(3-fluoropropyloxy)cyclohexane. This product was recrystallized twice from 6 ml of ethanolin a freezer to obtain 1.60 g (yield 58%) of4-(4-propylcyclohexyl)-(3-fluoropropyloxy)cyclohexane. Several kinds ofspectra well supported its structure.

¹ H-NMR (TMS internal standard) δ (ppm): 4.53 (dt, 2H), 3.57 (t, 2H),3.13 (m, 1H), 2.20-0.78 (m, 28H)

GC-MS: 284 (M+)

Cr 22.7 SB 64.1 Iso

The following compounds (No. 208 through No. 229) were producedaccording to the method in Example 6.Each of the compounds are indicatedby excerpting parameters R₁, Q, and --O (CH₂)_(n) CF₂ in the same way asdescribed before.

    ______________________________________                                                                             Phase                                    Com-                                 transi-                                  pound                                tion                                     No.   R.sub.1        I     --O(CH.sub.2)nCFH.sub.2                                                                 point                                    ______________________________________                                        208   C.sub.2 H.sub.5                                                                              0     --OCH.sub.2 CFH.sub.2                              209   C.sub.2 H.sub.5                                                                              0     --O(CH.sub.2).sub.2 CFH.sub.2                      210   C.sub.3 H.sub.7                                                                              0     --CCH.sub.2 CFH.sub.2                                                                   Cr 53.4 Iso                              211   C.sub.3 H.sub.7                                                                              0     --O(CH.sub.2).sub.2 CFH.sub.2                                                           Cr 22.7                                                                       SB 64.1 Iso                              212   C.sub.3 H.sub.7                                                                              0     --O(CH.sub.2).sub.3 CFH.sub.2                      213   C.sub.4 H.sub.9                                                                              0     --OCH.sub.2 CFH.sub.2                              214   C.sub.4 H.sub.9                                                                              0     --O(CH.sub.2).sub.3 CFH.sub.2                      215   C.sub.5 H.sub.11                                                                             0     --OCH.sub.2 CFH.sub.2                                                                   Cr 53.2                                                                       SB 68.1 Iso                              216   C.sub.5 H.sub.11                                                                             0     --O(CH.sub.2).sub.2 CFH.sub.2                      217   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           0     --OCH.sub.2 CFH.sub.2                              218   C.sub.3 H.sub.7 CH═CH--                                                                  0     --O(CH.sub.2).sub.2 CFH.sub.2                      219   C.sub.2 H.sub.5                                                                              1     --OCH.sub.2 CFH.sub.2                              220   C.sub.2 H.sub.5                                                                              1     --O(CH.sub.2).sub.2 CFH.sub.2                      221   C.sub.3 H.sub.7                                                                              1     --OCH.sub.2 CFH.sub.2                              222   C.sub.3 H.sub.7                                                                              1     --O(CH.sub.2).sub.2 CFH.sub.2                      223   C.sub.3 H.sub.7                                                                              1     --O(CH.sub.2).sub.3 CFH.sub.2                      224   C.sub.4 H.sub.9                                                                              1     --OCH.sub.2 CFH.sub.2                              225   C.sub.4 H.sub.9                                                                              1     --O(CH.sub.2).sub.3 CFH.sub.2                      226   C.sub.5 H.sub.11                                                                             1     --OCH.sub.2 CFH.sub.2                                                                   Cr30.4SB                                                                      78.1 Iso                                 227   C.sub.5 H.sub.11                                                                             1     --O(CH.sub.2).sub.2 CFH.sub.2                      228   C.sub.3 H.sub.7 CH═CH--                                                                  1     --OCH.sub.2 CFH.sub.2                              229   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --O(CH.sub.2).sub.2 CFH.sub.2                      ______________________________________                                    

While the clearing point of the compound No. 210 was 53.4° C., it can beunderstood that the value is higher compared with the clearing point of46° C. of the known bicyclohexane type compound having the samestructure except that the alkoxy group at the end of molecule is notsubstituted with a fluorine atom (reference is made to Examined JapanesePatent Publication No. 5-020418). Also, while the clearing point of thecompound No. 215 was 68.1° C., it can be understood that the value ishigher compared with the clearing point of 63° C. of the knownbicyclohexane type compound having the same structure except that thealkoxy group at the end of molecule is not substituted with a fluorineatom (reference is made to Examined Japanese Patent Publication No.5-020418).

Example 7

Production of 4-(4-propylcyclohexyl)-(1,1-difluoro-1-methoxy)cyclohexane(Compound expressed by the formula (1) wherein R₁ is C₃ H₇, X is F, Y ismethoxy, Q=0, m, n, and p are 2.(Compound No. 231))

First Stage

A mixture of 26.6 g (0.1 mole) of 4-(4-propylcyclohexyl) cyclohexanecarboxylic acid methyl ester produced according to the method forobtaining compound (11) mentioned in scheme (6)-(13), 40.4 g (0.1 mol)of Lawson reagent, and 100 ml of toluene was heated for 71 hours toreflux. Then, the solution was put in 100 ml of an ice water and theorganic layer thus separated was washed with water thrice, and driedover anhydrous magnesium sulfate. After the magnesium sulfate wasseparated, the solvent was distilled off under a reduced pressure, andthe residue thus obtained was recrystallized from 50 ml of ethanol toobtain 9.6 g (yield 34%) of a thioester. Melting point: 77.5° C.

Second stage

A mixture of 9.6 g (34 mmol) of the thioester obtained in the firststage, 10.9 g (68 mmol) of DAST, and 50 ml of dichloromethane wasstirred for 4 hours at a room temperature. The reaction product was putin 100 ml of an ice water and then extracted with 100 ml of toluene. Theorganic layer was washed twice with water and dried over anhydrousmagnesium sulfate. After the magnesium sulfate was separated, thesolvent was distilled off under a reduced pressure, and the residue thusobtained was subjected to a silica gel column chromatography (eluate:heptane) to obtain a crude product of4-(4-propylcyclohexyl)-(1,1-difluoro-1-methoxy)cyclohexane. This productwas recrystallized twice from 5 ml of ethanol in a freezer to obtain0.58 g (yield 6%) of4-(4-propylcyclohexyl)-(1,1-difluoromethoxy)cyclohexane. Several kindsof spectra well supported its structure.

¹ H-NMR (TMS internal standard) δ (ppm): 3.51 (s, 3H), 2.05-0.62 (m,27H)

GC-MS: 288 (M+)

Cr 51.5 SB 90.8 Iso

It can be understood that the clearing point 90.8° C. mentioned above isconsiderably higher compared with the clearing point of 52.0° C. of theknown bicyclohexane type compound having the same structure except thatthe methoxy substituted alkyl group at the end of molecule is notsubstituted with a fluorine atom (reference is made to Examined JapanesePatent Publication No. 62-005415).

The following compounds (No. 230 through No. 251) were producedaccording to the method in Example 7.Each of the compounds are indicatedby excerpting parameters R₁, Q, and --(O)_(m) (CH₂)_(n) CF₂ OR in thesame way as described before.

    ______________________________________                                        Com-                                Phase                                     pound                               transition                                No.   R.sub.1     I     --(O)m(CH.sub.2)nCF.sub.2 OR                                                              point                                     ______________________________________                                        230   C.sub.2 H.sub.5                                                                           0     --(CH.sub.2).sub.2 CF.sub.2 OMe                       231   C.sub.3 H.sub.7                                                                           0     --CF.sub.2 OMe                                                                            Cr 51.5 SB                                                                    90.8 Iso                                  232   C.sub.3 H.sub.7                                                                           0     --CF.sub.2 OEt                                        233   C.sub.3 H.sub.7                                                                           0     --CH.sub.2 CF.sub.2 OMe                               234   C.sub.3 H.sub.7                                                                           0     --O(CH.sub.2).sub.2 CF.sub.2 OMe                      235   C.sub.4 H.sub.9                                                                           0     --CH.sub.2 CF.sub.2 OMe                                                                   Cr 5.2 SB                                                                     78.1 Iso                                  236   C.sub.4 H.sub.9                                                                           0     --(CH.sub.2).sub.2 CF.sub.2 OEt                       237   C.sub.5 H.sub.11                                                                          0     --O(CH.sub.2).sub.2 CF.sub.2 OMe                      238   C.sub.5 H.sub.11                                                                          0     --O(CH.sub.2).sub.3 CF.sub.2 OMe                      239   C.sub.5 H.sub.11                                                                          0     --CH.sub.2 CF.sub.2 OMe                               240   C.sub.3 H.sub.7 CH═CH--                                                               0     --CF.sub.2 OEt                                        241   C.sub.2 H.sub.5                                                                           1     --(CH.sub.2).sub.2 CF.sub.2 OMe                       242   C.sub.2 H.sub.5                                                                           1     --CF.sub.2 OMe                                        243   C.sub.3 H.sub.7                                                                           1     --CF.sub.2 OEt                                        244   C.sub.3 H.sub.7                                                                           1     --CH.sub.2 CF.sub.2 OMe                               245   C.sub.3 H.sub.7                                                                           1     --O(CH.sub.2).sub.2 CF.sub.2 OMe                      246   C.sub.4 H.sub.9                                                                           1     --CH.sub.2 CF.sub.2 OMe                               247   C.sub.4 H.sub.9                                                                           1     --(CH.sub.2).sub.2 CF.sub.2 OEt                       248   C.sub.5 H.sub.11                                                                          1     --O(CH.sub.2).sub.2 CF.sub.2 OMe                      249   C.sub.5 H.sub.11                                                                          1     --O(CH.sub.2).sub.3 CF.sub.2 OMe                      250   C.sub.5 H.sub.11                                                                          1     --CH.sub.2 CF.sub.2 OMe                               251   C.sub.3 H.sub.7 CH═CH--                                                               1     --CF.sub.2 OEt                                        ______________________________________                                    

EXAMPLE 8

Production of 4-(4-(3-butenyl)cyclohexyl)-(3-fluoropropyl) cyclohexane(Compound expressed by the formula (1) wherein R₁ is CH₂ ═CHCH₂ CH₂ --,X and Y are H, Q and m are 0, n is 2, and p is 0. (Compound No. 256))

First Stage

A solution of DAIBAL (0.1 mol) in 100 ml of THF (concentration: 1mol/liter) was added dropwise to a solution of 30.6 g (0.1 mol) of2-(4-(4-(3-butenyl)cyclohexyl)cyclohexyl) propionic acid methyl producedaccording to the method of Unexamined Japanese Patent Publication No.1-151531 and dissolved in 100 ml of THF at a temperature of lower than-50° C., and stirred for 1 hour at the same temperature. The reactionliquid was put in 100 ml of an aqueous solution saturated with ammoniumchloride and then extracted with 200 ml of toluene. The organic layerwas washed with water thrice and dried over anhydrous magnesium sulfate.After the magnesium sulfate was separated and the solvent was distilledoff under a reduced pressure, the residue was recrystallized from 60 mlof ethanol to obtain 25.5 g (yield 90%) of4-(4-(3-butenyl)cyclohexyl)-(3-hydroxypropyl)cyclohexane. Several kindsof spectra well supported its structure.

Second stage

A mixture of 2.8 g (10 mmol) of the 4-(4-(3-butenyl)cyclohexyl)-(3-hydroxypropyl)cyclohexane obtained in the first stage,3.2 g (20 mmol) of DAST, and 20 ml of dichloromethane was stirred for 4hours at a room temperature. The reaction product was put in 50 ml of anice water and then extracted with 50 ml of toluene. The organic layerwas washed twice with water and dried over anhydrous magnesium sulfate.After the magnesium sulfate was separated, the solvent was distilled offunder a reduced pressure, and the residue thus obtained was subjected toa silica gel column chromatography (eluate: toluene), and recrystallizedtwice from 5 ml of ethanol in a freezer to obtain 0.64 g (yield 23%) of4-(4-(3-butenyl)cyclohexyl)-(3-fluoropropyl)cyclohexane. Several kindsof spectra well supported its structure.

The following compounds (No. 252 through No. 343) were producedaccording to the method in Example 8.Each of the compounds are indicatedby excerpting parameters R₁, Q, and --(CH₂)_(n) CFXH in the same way asdescribed before.

    ______________________________________                                        Com-                                 Phase                                    pound                                transition                               No.   R.sub.1        I     --(CH.sub.2)nCFXH                                                                       point                                    ______________________________________                                        252   C.sub.3 H.sub.7 CH═CH--                                                                  0     --CH.sub.2 CFH.sub.2                                                                    SB 85.5 Iso                              253   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --CH.sub.2 CFH.sub.2                                                                    SB 66.2 Iso                              254   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --CH.sub.2 CFH.sub.2                               255   C.sub.2 H.sub.5 CH═CH--                                                                  0     --(CH.sub.2).sub.2 CFH.sub.2                       256   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           0     --(CH.sub.2).sub.2 CFH.sub.2                       257   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --(CH.sub.2).sub.2 CFH.sub.2                       258   CH.sub.3 CH═CHCH.sub.2 O--                                                               0     --(CH.sub.2).sub.2 CFH.sub.2                       259   CH.sub.2 ═CHC.sub.2 H.sub.4 O---                                                         0     --(CH.sub.2).sub.2 CFH.sub.2                       260   CH.sub.2 ═OHCH.sub.2 OCH.sub.2 --                                                        0     --(CH.sub.2).sub.2 CFH.sub.2                       261   CH.sub.2 ═CHOCH.sub.2 --                                                                 0     --(CH.sub.2).sub.2 CFH.sub.2                       262   CH.sub.2 ═CHCH.sub.2 O--                                                                 0     --(CH.sub.2).sub.2 CFH.sub.2                       263   C.sub.2 H.sub.5 CH═CH--                                                                  0     --(CH.sub.2).sub.3 CFH.sub.2                       264   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           0     --(CH.sub.2).sub.3 CFH.sub.2                       265   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --(CH.sub.2).sub.3 CFH.sub.2                       266   CH.sub.3 CH═CHCH.sub.2 O--                                                               0     --(CH.sub.2).sub.3 CFH.sub.2                       267   CH.sub.2 ═CHC.sub.2 H.sub.4 O--                                                          0     --(CH.sub.2).sub.3 CFH.sub.2                       268   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --(CH.sub.2).sub.3 CFH.sub.2                       269   CH.sub.2 ═CHOCH.sub.2 --                                                                 0     --(CH.sub.2).sub.3 CFH.sub.2                       270   CH.sub.2 ═CHCH.sub.2 O--                                                                 0     --(CH.sub.2).sub.3 CFH.sub.2                       271   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           0     --(CH.sub.2).sub.4 CFH.sub.2                       272   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --(CH.sub.2).sub.4 CFH.sub.2                       273   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --(CH.sub.2).sub.4 CFH.sub.2                       274   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --(CH.sub.2).sub.5 CFH.sub.2                       275   C.sub.2 H.sub.5 CH═CH--                                                                  0     --CH.sub.2 CF.sub.2 H                              276   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --CH.sub.2 CF.sub.2 H                              277   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --CH.sub.2 CF.sub.2 H                              278   C.sub.2 H.sub.5 CH═CH--                                                                  0     --(CH.sub.2).sub.2 CF.sub.2 H                      279   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           0     --(CH.sub.2).sub.2 CF.sub.2 H                      280   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --(CH.sub.2).sub.2 CF.sub.2 H                      281   CH.sub.3 CH═CHCH.sub.2 O--                                                               0     --(CH.sub.2).sub.2 CF.sub.2 H                      282   CH.sub.2 ═CHC.sub.2 H.sub.4 O--                                                          0     --(CH.sub.2).sub.2 CF.sub.2 H                      283   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --(CH.sub.2).sub.2 CF.sub.2 H                      284   CH.sub.2 ═CHOCH.sub.2 --                                                                 0     --(CH.sub.2).sub.2 CF.sub.2 H                      285   CH.sub.2 ═CHCH.sub.2 O--                                                                 0     --(CH.sub.2).sub.2 CF.sub.2 H                      286   C.sub.2 H.sub.5 CH═CH--                                                                  0     --(CH.sub.2).sub.3 CF.sub.2 H                      287   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           0     --(CH.sub.2).sub.3 CF.sub.2 H                      288   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --(CH.sub.2).sub.3 CF.sub.2 H                      289   CH.sub.3 CH═CHCH.sub.2 O--                                                               0     --(CH.sub.2).sub.3 CF.sub.2 H                      290   CH.sub.2 ═CHC.sub.2 H.sub.4 O--                                                          0     --(CH.sub.2).sub.3 CF.sub.2 H                      291   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --(CH.sub.2).sub.3 CF.sub.2 H                      292   CH.sub.2 ═CHOCH.sub.2 --                                                                 0     --(CH.sub.2).sub.3 CF.sub.2 H                      293   CH.sub.2 ═CHCH.sub.2 O--                                                                 0     --(CH.sub.2).sub.3 CF.sub.2 H                      294   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           0     --(CH.sub.2).sub.4 CF.sub.2 H                      295   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --(CH.sub.2).sub.4 CF.sub.2 H                      296   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        0     --(CH.sub.2).sub.4 CF.sub.2 H                      297   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         0     --(CH.sub.2).sub.5 CF.sub.2 H                      298   C.sub.2 H.sub.5 CH═CH--                                                                  1     --CH.sub.2 CFH.sub.2                               299   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --CH.sub.2 CFH.sub.2                               300   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --CH.sub.2 CFH.sub.2                               301   C.sub.2 H.sub.5 CH═CH--                                                                  1     --(CH.sub.2).sub.2 CFH.sub.2                       302   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           1     --(CH.sub.2).sub.2 CFH.sub.2                       303   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --(CH.sub.2).sub.2 CFH.sub.2                       304   CH.sub.3 CH═CHCH.sub.2 O--                                                               1     --(CH.sub.2).sub.2 CFH.sub.2                       305   CH.sub.2 ═CHC.sub.2 H.sub.4 O--                                                          1     --(CH.sub.2).sub.2 CFH.sub.2                       306   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --(CH.sub.2).sub.2 CFH.sub.2                       307   CH.sub.2 ═CHOCH.sub.2 --                                                                 1     --(CH.sub.2).sub.2 CFH.sub.2                       308   CH.sub.2 ═CHCH.sub.2 O--                                                                 1     --(CH.sub.2).sub.2 CFH.sub.2                       309   C.sub.2 H.sub.5 CH═CH--                                                                  1     --(CH.sub.2).sub.3 CFH.sub.2                       310   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           1     --(CH.sub.2).sub.3 CFH.sub.2                       311   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --(CH.sub.2).sub.3 CFH.sub.2                       312   CH.sub.3 CH═CHCH.sub.2 O--                                                               1     --(CH.sub.2).sub.3 CFH.sub.2                       313   CH.sub.2 ═CHC.sub.2 H.sub.4 O--                                                          1     --(CH.sub.2).sub.3 CFH.sub.2                       314   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --(CH.sub.2).sub.3 CFH.sub.2                       315   CH.sub.2 ═CHOCH.sub.2 --                                                                 1     --(CH.sub.2).sub.3 CFH.sub.2                       316   CH.sub.2 ═CHCH.sub.2 O--                                                                 1     --(CH.sub.2).sub.3 CFH.sub.2                       317   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           1     --(CH.sub.2).sub.4 CFH.sub.2                       318   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --(CH.sub.2).sub.4 CFH.sub.2                       319   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --(CH.sub.2).sub.4 CFH.sub.2                       320   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --(CH.sub.2).sub.5 CFH.sub.2                       321   C.sub.2 H.sub.5 CH═CH--                                                                  1     --CH.sub.2 CFH.sub.2                               322   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --CH.sub.2 CFH.sub.2                               323   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --CH.sub.2 CFH.sub.2                               324   C.sub.2 H.sub.5 CH═CH--                                                                  1     --(CH.sub.2).sub.2 CFH.sub.2                       325   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           1     --(CH.sub.2).sub.2 CFH.sub.2                       326   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --(CH.sub.2).sub.2 CFH.sub.2                       327   CH.sub.3 CH═CHCH.sub.2 O--                                                               1     --(CH.sub.2).sub.2 CFH.sub.2                       328   CH.sub.2 ═CHC.sub.2 H.sub.4 O--                                                          1     --(CH.sub.2).sub.2 CFH.sub.2                       329   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --(CH.sub.2).sub.2 CFH.sub.2                       330   CH.sub.2 ═CHOCH.sub.2 --                                                                 1     --(CH.sub.2).sub.2 CFH.sub.2                       331   CH.sub.2 ═CHCH.sub.2 O--                                                                 1     --(CH.sub.2).sub.2 CFH.sub.2                       332   C.sub.2 H.sub.5 CH═CH--                                                                  1     --(CH.sub.2).sub.3 CFH.sub.2                       333   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           1     --(CH.sub.2).sub.3 CFH.sub.2                       334   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --(CH.sub.2).sub.3 CFH.sub.2                       335   CH.sub.3 CH═CHCH.sub.2 O--                                                               1     --(CH.sub.2).sub.3 CFH.sub.2                       336   CH.sub.2 ═CHC.sub.2 H.sub.4 O--                                                          1     --(CH.sub.2).sub.3 CFH.sub.2                       337   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --(CH.sub.2).sub.3 CFH.sub.2                       338   CH.sub.2 ═CHOCH.sub.2 --                                                                 1     --(CH.sub.2).sub.3 CFH.sub.2                       339   CH.sub.2 ═CHCH.sub.2 O--                                                                 1     --(CH.sub.2).sub.3 CFH.sub.2                       340   CH.sub.2 ═CHC.sub.2 H.sub.4 --                                                           1     --(CH.sub.2).sub.4 CFH.sub.2                       341   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --(CH.sub.2).sub.4 CFH.sub.2                       342   CH.sub.2 ═CHCH.sub.2 OCH.sub.2 --                                                        1     --(CH.sub.2).sub.4 CFH.sub.2                       343   CH.sub.3 CH═CHC.sub.2 H.sub.4 --                                                         1     --(CH.sub.2).sub.5 CFH.sub.2                       ______________________________________                                    

EXAMPLE 9 (Use Example 1)

Nematic liquid crystal composition ZLI-1132 produced by Merck GmbH,comprising a cyanophenylcyclohexane type liquid crystal compound, andhaving a clearing point of 72.4° C., value of dielectric anisotropy (Δε)of 11.0, value of optical anisotropy (Δn) of 0.137, viscosity of 27.0cP, and threshold voltage at a cell thickness of 9 μ of 1.78 V was addedwith the compound of Example 6,4-(4-propylcyclohexyl)-(3-fluoropropyloxy)cyclohexane in an amount of15% by weight to obtain a nematic liquid crystal composition. Each valueof the physical properties were as follows:

Clearing point: 66.6° C., Δε: 9.6, Δn: 0.121, viscosity: 23.6 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.70 V

EXAMPLE 10 (Use Example 2)

A nematic liquid crystal composition was obtained in the same proceduresas in Example 9 except that the compound of Example 7,4-(4-propylcyclohexyl)-(1,1-difluoro-1-methoxy) cyclohexane was used inplace of the compound of Example 6. Each value of the physicalproperties were as follows:

Clearing point: 69.1° C., Δε: 9.6, Δn: 0.124, viscosity: 28.2 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.75 V

EXAMPLE 11 (Use Example 3) through Example 26 (Use Example 18)

Sixteen kinds of nematic liquid crystal compositions were obtained inthe same procedure as in Example 9 except that the compound No. 1, 2, 3,4, 6, 7, 14, 35, 52, 53, 60, 141, 215, 226, 235, or 252 was used. Thevalue of physical properties of each of the compositions were asfollows:

Example 11 (Compound of No. 1 was used)

Clearing point: 60.5° C., Δε: 9.2, Δn: 0.119, viscosity: 25.3 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.59 V

Example 12 (Compound of No. 2 was used)

Clearing point: 66.7° C. , Δε: 9.4, Δn: 0.122, and viscosity: 25.1 cP

EXAMPLE 13 (Compound of No. 3 was used)

Clearing point: 64.4° C., Δε: 9.3, Δn: 0.119, viscosity: 25.6 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.63 V

EXAMPLE 14 (Compound of No. 4 was used) Clearing point: 65.6° C., Δε:9.3, Δn: 0.121, viscosity: 26.4 cP, and threshold voltage at a cellthickness of 8.7 μ: 1.66 V EXAMPLE 15 (Compound of No. 6 was used)

Clearing point: 68.9° C., Δε: 9.5, Δn: 0.123, viscosity: 25.6 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.75 V

EXAMPLE 16 (Compound of No. 7 was used)

Clearing point: 68.3° C., Δε: 9.6, Δn: 0.122, viscosity: 25.6 cP, andthreshold voltage at a cell thickness of 8.8 μ: 1.74 V

EXAMPLE 17 (Compound of No. 14 was used)

Clearing point: 68.7° C., Δε: 9.5, Δn: 0.122, viscosity: 24.4 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.64 V

EXAMPLE 18 (Compound of No. 35 was used)

Clearing point: 67.4° C., Δε: 9.6, Δn: 0.121, viscosity: 25.7 cP, andthreshold voltage at a cell thickness of 8.8 μ: 1.72 V

EXAMPLE 19 (Compound of No. 52 was used)

Clearing point: 72.8° C., Δε: 9.4, Δn: 0.123, viscosity: 22.9 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.77 V

EXAMPLE 20 (Compound of No. 53 was used)

Clearing point: 71.3° C., Δε: 9.4, Δn: 0.123, viscosity: 23.9 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.77 V

EXAMPLE 21 (Compound of No. 60 was used)

Clearing point: 72.3° C., Δε: 9.5, Δn: 0.122, viscosity: 23.6 cP, andthreshold voltage at a cell thickness of 8.8 μ: 1.81 V

EXAMPLE 22 (Compound of No. 141 was used)

Clearing point: 65.3° C., Δε: 10.0, Δn: 0.120, viscosity: 23.9 cP, andthreshold voltage at a cell thickness of 8.8 μ: 1.76 V

EXAMPLE 23 (Compound of No. 215 was used)

Clearing point: 67.7° C., Δε: 9.7, Δn: 0.122, viscosity: 24.6 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.73 V

EXAMPLE 24 (Compound of No. 226 was used)

Clearing point: 66.4° C., Δε: 9.6, Δn: 0.122, viscosity: 24.9 cP, andthreshold voltage at a cell thickness of 8.8 μ: 1.74 V

EXAMPLE 25 (Compound of No. 235 was used)

Clearing point: 69.1° C., Δε: 9.6, Δn: 0.124, viscosity: 28.2 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.75 V

EXAMPLE 26 (Compound of No. 252 was used)

Clearing point: 66.7° C., Δε: 9.6, Δn: 0.122, viscosity: 22.1 cP, andthreshold voltage at a cell thickness of 8.7 μ: 1.69 V

According to the present invention, when a fluorine atom was introducedin an alkyl or alkoxy group at the end of the molecule in, for example,bicyclohexane type compounds or cyclohexylethylcyclohexane typecompounds, clearing point of liquid crystal compositions comprising thecompound is considerably raised. Since the compounds of the presentinvention are also intended to be used as a viscosity decreasing agent,the compounds can usually be mixed with a liquid crystal composition ina mixing ratio of several tens % when the compounds are actually used.Thus, the difference in clearing point of a single compound exactlycomes to considerably affect the clearing of compositions. In thissense, development of the compounds of the present invention which havea high clearing point is extremely useful.

Availability in Industry

Liquid crystal compositions are provided which are suitable for use inliquid crystal display devices, have a high clearing point, and have afunction of decreasing viscosity. Also, novel liquid crystallinecompounds useful as a component of the liquid crystal compositions areprovided.

What is claimed is:
 1. A liquid crystalline compound expressed by thegeneral formula (1) ##STR20## wherein R₁ is an alkyl group having 1 to12 carbon atoms and one CH₂ group in the alkyl group may be replaced byoxygen atom or --CH═CH--; X represents hydrogen atom or fluorine atom; Yrepresents hydrogen atom or alkoxy group having 1 to 5 carbon atoms; land m independently represent 0 or 1, respectively; and n and pindependently represent an integer of 0 to 10, respectively, and when pis 0, n is 2 or more, and when Y is an alkoxy group, X is fluorine atomand p is 0, provided that in no case X is fluorine atom, p is 0, and Yis hydrogen atom when m is
 0. 2. A liquid crystalline compound expressedby the general formula (1) ##STR21## wherein R₁ is an alkyl group having1 to 12 carbon atoms and one CH₂ group in the alkyl group may bereplaced by oxygen atom or --CH═CH--; X represents a fluorine atom; Yrepresents an alkoxy group having 1 to 5 carbon atoms; l and mindependently represent 0 or 1, respectively; n represents an integer of2 to 10; and p is
 0. 3. A liquid crystalline compound expressed bygeneral formula (1) ##STR22## wherein R₁ is an alkyl group having 1 to12 carbon atoms and one CH₂ group in the alkyl group may be replaced byoxygen atom or --CH═CH--; X represents a hydrogen atom or flourine atom;Y represents a hydrogen atom or an alkoxy group having 1 to 5 carbonatoms; l represents 0 or 1; m is 0; n represent an integer of 0 to 10;and p is
 1. 4. A liquid crystalline compound expressed by the generalformula (1) ##STR23## wherein R₁ is an alkyl group having 1 to 12 carbonatoms and one CH₂ group in the alkyl group may be replaced by oxygenatom or --CH═CH--; X represents a hydrogen atom or fluorine atom; Yrepresents a hydrogen atom or an alkoxy group having 1 to 5 carbonatoms; l represents 0 or 1: m is 1: n represents an integer of 0 to 10;and p is
 1. 5. The liquid crystalline compound according to claim 1wherein m is
 0. 6. The liquid crystalline compound according to claim 1wherein m is
 1. 7. The liquid crystalline compound according to claim 1wherein Y is hydrogen atom.
 8. The liquid crystalline compound accordingto claim 5 wherein p is
 0. 9. The liquid crystalline compound accordingto claim 6 wherein p is
 0. 10. A liquid crystal composition comprisingtwo or more components at least one of which is a compound according toany one of claims 1, 2, 3, 4, 6,
 8. 11. A liquid crystal compositioncontaining, as a first component, at least one compound according to anyone of claims 1 to 4, 6, 8, or 2-4 and containing, as a secondcomponent, one or more compounds selected from the group consisting ofthe following general formulas (II), (III), and (IV) ##STR24## whereinR₂ represents an alkyl group having 1 to 10 carbon atoms, Z represents For Cl, Q₁ and Q₂ independently represent H or F, respectively, rrepresents 1 or 2, and Z₁ and Z₂ independently represent --CH₂ CH₂ -- orcovalent bond.
 12. A liquid crystal composition containing, as a firstcomponent, at least one compound according to any one of claims 1 to 4,6, 8, or 2-4 and containing, as a second component, one or morecompounds selected from the group consisting of the following generalformulas (V), (VI), (VII), (VIII), and (IX) ##STR25## wherein R₃represents an alkyl group having 1 to 10 carbon atoms or an alkenylgroup having 2 to 10 carbon atoms, methylene groups which are notadjacent to each other in these groups may be replaced by oxygen atom,Z₃ represents --CH₂ CH₂ --, --COO--, or covalent bond, Q₃ represents Hor F, A represents a cyclohexane ring, benzene ring, or 1,3-dioxanering, and s represents 0 or 1, ##STR26## wherein R₄ represents an alkylgroup having 1 to 10 carbon atoms, Q₄ represents H or F, and krepresents 0 or 1, ##STR27## wherein R₅ represents alkyl group having 1to 10 carbon atoms, B represents cyclohexane ring or benzene ring, Q₅represents H or F, Z₄ represents --COO-- or covalent bond, and hrepresents 0 or 1, ##STR28## wherein R₆ and R₇ independently representan alkyl group, alkoxy group, or alkoxymethyl group each having 1 to 10carbon atoms, K represents cyclohexane ring, pyrimidine ring, or benzenering, D represents cyclohexane ring or benzene ring, and Z₅ represents--C.tbd.C--, --COO--, --CH₂ CH₂ --, or covalent bond, ##STR29## whereinR₈ represents an alkyl group or alkoxy group each having 1 to 10 carbonatoms, R₉ represents an alkyl group, alkoxy group, or alkoxymethyl groupeach having 1 to 10 carbon atoms, E represents cyclohexane ring orpyrimidine ring, G and J independently represent cyclohexane ring orbenzene ring, respectively, Z₆ represents --COO--, --CH₂ CH₂ --, orcovalent bond, Z₇ represents --C.tbd.C--, --COO--, or covalent bond, andQ₆ represents H or F.
 13. A liquid crystal display device comprising aliquid crystal composition comprising two or more components at leastone of which is a compound according to any one of claims 1 to 7, 8, 9or 2-4.
 14. A liquid crystal display device comprising a liquid crystalcomposition according to claim
 10. 15. A liquid crystal display devicecomprising a liquid crystal composition according to claim
 11. 16. Aliquid crystal display device comprising a liquid crystal compositionaccording to claim 12.